TW201105694A - Urethane (metah) acrylate compound and resin composition containing such compound - Google Patents

Abstract

This invention provides urethane (metha) acrylate compound (A) which is obtained by reacting the following (I) and (II) (I) any one of the following (i), (ii), or (iii): (i) dipentaerythritol poly (metha) acrylate (a) mixture having a hydroxyl value of 80 to 120 mg KOH/g (hereinafter referred to as mixture (a)), the mixture (a) containing at least 2 of the compounds selected from the group consisting of dipentaerythritol tri (metha) acrylate, dipentaerythritol tetra (metha) acrylate, dipentaerythritol penta (metha) acrylate, and dipentaerythtol hexa (metha) acrylate, (ii) both of the mixture (a) and a glycerin; or (iii) all three of the mixture (a), the glycerin and a (metha) acrylate of C2 to C5 aliphatic poly (2 to 4)ol, and (II) a polyisocyanate compound (b) containing a diisocyanate compound. This invention also provides a resin composition containing the urethane (metha) acrylate compound (A) and a photo-polymerizing initiator (C), a cured article of the resin composition, a hard coating agent and a hard coating. The hard coating film obtained by curing the resin composition has excellent handness, ahesion, strength against scratch, and such properties of avoiding curlings and crackings.

Description

201105694 VI. Description of the Invention: [Technical Field] The present invention relates to an urethane (fluorenyl) acrylate compound (A), a resin composition comprising the same, and particularly comprising the amine vinegar (曱) a resin composition of the acrylate compound (A) and a photopolymerization initiator, and a cured film of the resin composition. The amine ester (mercapto) acrylate compound (A) is obtained by using the following components as a raw material: At least two of the group consisting of free dipentaerythritol tris(decyl) acrylate, dipentaerythritol tetrakis(meth) acrylate, dipentaerythritol penta(indenyl) acrylate, and dipentaerythritol hexakisyl acrylate And the hydroxyl value is 80 to uomgKOH / g of a pentaerythritol poly(meth) propyl acrylate (dipentaerythritol poly (metha) acrylate) mixture (a). Further, the cured film of the resin composition of the present invention is excellent in hardness, adhesion to a substrate, scratch resistance, etc., and has small curl and little occurrence of cracks, so it can be used as a plastic film or a small frame. Hard coat of the body. [Ulethane is available in various ways such as amino phthalic acid ester, urethane ethyl ester, polyurethane, amine ester, etc., and the stalk herein is amine S]. Further, since the cured film of the resin composition of the present invention has good adhesion to the substrate, has high hardness, and has moderate flexibility, the resin composition of the present invention can also be used for a color filter. (For example, color filters used in color liquid crystal displays, color cameras, color digital cameras, electronic paper, etc.), black matrices, or spacers. [Prior Art] At present, it is excellent in various properties such as workability, transparency, and optical characteristics. 322127 4 201105694 A lightweight, inexpensive plastic is softer than glass, and has an effective use in one. However, the J plastic surface is coated with a hard coating agent. Hard = surface is easy to hurt and other shortcomings - so - general coatings, acrylic (four) n series are mainly known in many polyoxic oxygen systems, polysulfuric oxide hard coating agents are due to thermal curing of amine coatings By. It is mainly used. However, the polylithic oxygen system has excellent cold quality and has been disadvantaged ever since. "The hard coating agent has a long hardening time and is high. Therefore, as a hard coating agent which compensates for the disadvantages of the development of the polyfluorene oxygen system and the use of the photosensitive propylene-based agent, the acrylic hard coating agent is patented by K. The document U is processed, so the processing speed is 22, and the radiation of hard households, sub-ultraviolet rays, etc. is immediately hard. Therefore, the propylene (four) is currently hard and inexpensive, and the acrylic hard coating agent j is Mainly in the field of hard coating. In the case of continuous processing, the surface of the substrate is coated with a plastic substrate film of the substrate of the material: arm and vinegar film, vinyl chloride film, three; : De-acrylic film, polycarbon, yttrium cellulose film, polyether 飒 (P〇lyetherSUlfQne) thin material. Among them, from the viewpoint of the characteristics of each woman, the most widely used film is poly. The film system can be used as a glass (4) film, or a car (four) fine, white surface thin surface antifouling film, etc., for electronic materials can be used as m flat TV, touch panel, liquid crystal display D ), functions in electrosurgical display (10) P), organic EL display, etc. In addition to the film, as the poly-resin molded product, the main body or switch of the home appliance I, the mobile phone or the personal computer, and the electronic device frame such as the player 322127 5 201105694 have been widely used. A hard coat layer is formed to prevent scratching of the surface. Further, a sheet or a substrate such as a hard-coated polycarbonate or acrylic is used for a liquid crystal related member around a disc or a backlight. In recent years, it has also been developed to be hard. The coating imparts a function other than the performance of the so-called scratch-resistant hard coat. For example, in displays such as crt, LCD, and PDP provided with a film, it is difficult to view the display surface due to reflection, and the eyes are easily fatigued. For example, in the case of the patent document 2, the development of the hard coat layer having the surface anti-reflection ability is being carried out. On the other hand, the hardness improvement of the original purpose of the hard coat layer is also studied. For example, in Patent Document 3 The hardness is improved by adding a polyfunctional amine acetoacetate to the resin composition. However, the polyfunctional amine acetoacetic acid vinegar used has a large hardening shrinkage. In the case of the resin composition for the hard coat layer of the antireflection material, a polyfunctional amine ester (mercapto) acrylate is used. , and it is not particularly satisfactory, and it is not necessarily satisfactory, and it is expected to be further improved. [Prior Patent Document] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 9-48934 [Patent Literature] [Patent Document 3] JP-A-2000-187102 (Patent Document 4) JP-A-2000-187102 (Summary of the Invention) (Problem to be solved by the Invention) 6 322127 201105694 The object of the present invention is to obtain a hardened film, an amine ester (meth) acrylate compound which can obtain the hardened film, and a resin composition containing the same, which is excellent in hardness and scratch resistance and curled and turtle The occurrence of cracks is also less, and is superior to those known above. (Means for Solving the Problems) The inventors of the present invention have achieved the present invention by conducting intensive studies in order to solve the above problems. That is, the present invention relates to the inventors described below. (1) An amine-based compound (A) which is a compound (A) which comprises (1) the following (0, (ii) or (iii) and (II) contain a diisocyanate The compound polyisocyanate compound (b) is obtained by the reaction: (1) comprising a di(pentaerythritol) tri(meth)acrylate, dipentaerythritol tetrakis(meth)acrylate, dipentaerythritol penta(indenyl)acrylate. And a dipentaerythritol poly(indenyl) acrylate mixture (a) having at least two of the group consisting of dipentaerythritol hexakis(meth)acrylate and having a hydroxyl value of 80 to 120 mgKOH/g (hereinafter referred to as the mixture (hereinafter) a)); (ii) both the mixture (a) and glycerin; or (iii) the mixture (a), glycerin and C2 to C5 aliphatic poly (2 to 4) alcohol (meth) acrylate (2) The amine ester (mercapto) acrylate compound (A) according to the above item (1), wherein (I) is (i) the mixture (a). (3) as in the above (1) or (2) an amine ester (mercapto) acrylate compound (A), wherein the '(II) polyisocyanate compound (b) is a diisocyanate compound Separately, or a combination of a compound of isocyanic acid and a compound of triisocyanate, 2 7 322127 201105694 The ratio of the isocyanate δ compound to the triisocyanate compound is relative to the diisocyanate S compound 1 mole The 'triisocyanate compound is a ratio of 〇 to 1 〇 mol. (4) The amine ester (mercapto) acrylate compound (Α) according to any one of the above items (1) to (3) As shown in formula (1)··

^—N~X~N—C~Yj-C—N—X—N~c—A

A η (wherein 'X is an isocyanate residue, n is an integer from 〇 to loo, and Υ is an organic group represented by the following formula (2), wherein a, b&c are 1^ respectively $4, 0$1^3 and 0 "^3 integers, and & + 1:) + (: = 4

(2) - 〇h2c ch2o - OH2C - i - CH2OCH2i - CH2 〇 - 〇 H2c ch2 〇 - and, A is an organic group represented by the above formula (2), wherein x is an isocyanate residue, C is an integer of 0, a and 〇gbg4, and a + b = 5, and B is an organic group represented by the above formula (2), wherein \ is an isocyanate residue 'c is O'a and b is the following (i) or (ii): (i) B is present at the end, where 3 and 1) are integers, and a+b=5, 322127 8 201105694 (Η)Β exists outside the end In the formula, a and b in the formula are BU4, (^b S3 is an integer ' and a+b=4). (5) A method for producing a (meth)acrylic acid hydrazone compound U) according to any one of the above items (1) to (4), which is a polyisocyanate having an active hydrogen group in the mixture (4). The ratio of the iso-acid vinegar group in the acid vinegar compound (8) is (1) (1) the mixture (4) is reacted with the (1)) polyiso-I acid ester compound (b) in an amount of from 0.1 to 50 equivalents. (6) The amine ester (meth) acrylate compound (1) according to the above item (1) or (3), wherein (I) is (ii) the mixture (^) and glycerin. (7) A method for producing an amine (indenyl) acrylate-based compound (A) according to the above item (6), which is based on an active hydrogen group in glycerol relative to an active hydrogen group in the mixture (4) The equivalent of 0 01 to 1 〇 equivalent, (II) the ratio of the isocyanate carboxylic acid equivalent in the acid-cooling compound (b) to the ratio of G. 1 to 5 G equivalent, such that the mixture of the above (1) (a) And glycerin are reacted with the (Π) polyisocyanate compound (b) of the above (1). (8) A resin composition comprising the (meth) acrylate compound (A), (meth) acetoacetate (8) and photopolymerization initiation of any one of the above items (1) to (4) and (8) Agent (C). (9) A resin composition according to the above item (8), which is used for a hard coat layer. (10) The amine ester (meth) acrylate compound (A) according to the above item (1) or (3) wherein (I) is (iii) the mixture (a), glycerin and C2 to C5 aliphatic plural ( 2 to 4) 3 of the alcohol (mercapto) acrylate. (1) A process for producing the aminoester (meth)propionate compound (A) of the above item (1) or (10), which is based on the active hydrogen group in the mixture (a) 322127 9 201105694 1 equivalent, the active hydrogen group equivalent of glycerol is 0.01 S 10 equivalents and the active hydrogen group equivalent of 01 to 10 of the (meth)acrylic acid g| of the C1 to C5 month 曰 (2 to 4) alcohol, 01 to 10, polyisocyanate The isocyanate group of the compound (b) is a ratio of 0.1 to 50 equivalents of the above-mentioned (1) (1) of (1). The compound (8), glycerin, and the (meth) acrylate of the C2 to C5 aliphatic polyvalent (2 to 4) alcohol are reacted with the polyisocyanate compound (b) of the above (1) (1)). (12) The amine ester (mercapto) acrylate compound (A) according to any one of the above items (1) to (4), (6) or (1), wherein, relative to the mixture (&) The total amount, the mixture (a) in (I), in the area ratio of high performance liquid chromatography (HpLC)»), contains dipentaerythritol penta (meth) acrylate 35 to 60% 'again The total of the three additions of dipentaerythritol tetrakis(meth)acrylate and dipentaerythritol hexa(meth)acrylate is 9〇 to 1〇〇%, and the remainder 0 to 10% is dipentaerythritol tris(fluorenyl). A acrylate of a polyvalent amount of acrylate and tripentaerythritol. (13) The amine ester (meth) acrylate compound (A) according to any one of the above (1) to (4), (6), 〇〇) or (12), wherein the polyisocyanate compound (b) ) is an isooxy acid-independent compound alone. (14) An amine ester (mercapto) acrylate compound as described in any one of the above items (1) to (3), (5), (6), (1), (12) or (13) (A) Wherein the polyisocyanate compound (b) is used in combination with a diisocyanate compound and a triisocyanate compound. (15) The amine ester (mercapto) acrylate compound (A) according to the above item (13) or (14), wherein the diisocyanate compound is hexamethylene diisocyanate. 10 322127 201105694 (16) The amine ester (mercapto) acrylate compound (A) according to any one of the above items (1) to (4), (6), (10) and (12) to (14), Wherein the mixture (a) is a mixture of dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, or dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate A mixture of an ester and dipentaerythritol hexaacrylate, the polyisocyanate compound (b) is hexamethylene diisocyanate alone or hexamethylene diisocyanate and hexamethylene diisocyanate 3. (Π) A resin composition comprising the amine ester (meth) acrylate of any one of the above items (1) to (4), (6), (10), and (12) to (16) Compound (A) and photopolymerization initiator (C). (18) A cured film of a resin composition comprising the amine ester of any one of the above (丨) to (4), (6), (10), and (12) to (16) An acrylate compound (A) and a photopolymerization initiator (C). (19) The amine ester (mercapto) acrylate compound (A) according to any one of the above items (1) to (4), (6), (10), and (12) to (16), wherein the viscosity (6 〇. 〇 is 5 to 40 Pa · s. (Effect of the invention) By using the amine ester (fluorenyl) acrylate compound (A) of the present invention, it is possible to provide a high transparency, hardness and resistance to a hardened film which is not apt to be damaged and which is not likely to be cracked, or a resin composition which can obtain a hardened film having high transparency, moderate hardness, flexibility and physical properties, and a cured product of the resin plant, and the resin The hard coating composed of the composition is a hard coating layer of the hard coating agent. Long-term use 322127 11 201105694 [Embodiment] The present invention will be described in detail below. ▲In the present invention, the use as a raw material is selected from the second quarter.戍tetraol III (Yinji) Acrylic vinegar, dipentaerythritol tetrakis(fluorenyl) propylene vinegar, dipentaerythritol penta (meth) acrylate vinegar and diquaternary stilbene hexa(methyl) acrylate acid At least two of the pentaerythritol poly(methyl) propylene vinegar Preferably, the composition comprises at least two pentaerythritols selected from the group consisting of dipentaerythritol triacetate vinegar, dipentaerythritol tetraacrylic acid vinegar, dipentaerythritol pentaacetic acid vinegar, and dipentaerythritol hexaacrylate. The base value of the polyacrylic acid g-type mixture (a,)} is in the range of 8 Å to 12 〇 mg KOH / g. When the hydroxy valence is in this range, gelation does not occur in the reaction of the amine esterification. Efficiently obtain the desired amine vinegar (meth) acrylate compound (A) {preferably urethane acrylate compound (A,)}. Further, the obtained amine ester (meth) acrylate compound can be obtained ( The resin composition of Α) obtains a hard coat layer having high hardness and excellent curl resistance and high flexibility. Further, in the present specification, when the above-mentioned amine ester (mercapto) acrylic acid must be distinguished by structure or composition In the case of an ester compound (Α), a compound which does not contain a skeleton derived from glycerol is referred to as an amine ester (mercapto) acrylate compound (Α1), and is referred to as an amine ester (mercapto) acrylate compound containing a skeleton derived from glycerin ( Α 2), contains A compound derived from a skeleton of glycerin and a skeleton derived from a (meth) acrylate of a C2 to C5 aliphatic polybasic (2 to 4) alcohol is referred to as an amine ester (mercapto) acrylate compound (A3). Raw material dipentaerythritol poly(indenyl)acrylic acid 12 322127 201105694 vinegar mixture (4) (hereinafter also referred to as poly(methyl) acrylate mixture (a) or the conjugate (a)) can be made by dipentaerythritol The dehydration condensation reaction is carried out with (meth)acrylic acid in the presence of a dehydration condensation catalyst, for example, an acid catalyst, and dipentaerythritol is obtained by subjecting (meth)(10) acid to the reaction. The mixture (a) is preferably selected. Group of free dipentaerythritol tris(meth)acrylic acid i day, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate vinegar and dipentaerythritol hexa(meth) acrylate vinegar At least three of them, and more preferably three types of dipentaerythritol tetra, penta and hexa (meth) acrylate. Typically, the mixture (a) is a mixture of four of dipentaerythritol tris, tetra, penta and hexa (meth) acrylates, or a mixture of three dipentaerythritol tetra, five and hexa (meth) acrylates. . The mixture (a) may be a polyvalent acrylate of three or more pentaerythritols such as dipentaerythritol which is formed by-produced in the above condensation reaction. Further, in the above (indenyl) acrylate of pentaerythritol, the acrylate (dipentaerythritol tri, tetra, penta and hexaacrylate) is more preferable than the methacrylate compound from the viewpoint of cost or the like. In the present invention, the content ratio of each component to the total amount of the mixture (a) is based on the area ratio (%) of high performance liquid chromatography (HPLC) as described below. The pentaerythritol penta (meth)acrylic acid S (preferably dipentaerythritol pentaacetic acid vinegar) is 30 to 70%, preferably 30 to 60%, more preferably 35 to 55% 'best line 35 to 50. % 'in the dipentaerythritol penta(indenyl) acrylate (preferably dipentaerythritol pentaacrylate) further added dipentaerythritol tetra and hexa (meth) acrylate (preferably dipentaerythritol tetra and hexapropane) The total of the three after 322127 13 201105694 can be 85 to 100%, preferably 90 to loo. %. In the above dehydration condensation reaction, when the by-product of the above-mentioned multicomponent is considered, the total of the above three is from 85 to 98%, more preferably from 90 to 97%. The remainder is a polyvalent acrylate comprising dipentaerythritol tris(mercapto) acrylate (preferably dipentaerythritol triacrylate) or/and a third amount or more of the above pentaerythritol. Further, at this time, the respective contents of dipentaerythritol tetrakis and hexa(meth) acrylate are preferably about 1 to 40% (preferably about 1 to 30%) and 15 to 40%, respectively. In the range of about 20 to 40%, the content of dipentaerythritol triacrylate is about 10%, preferably 5% or less (including zero). Others may also include the above-mentioned multi-component acrylate. The method for producing the above mixture (a) will be described in more detail below. The above mixture (a) used as a raw material in the present invention is not limited thereto. The acid catalyst used in the above dehydration condensation reaction may, for example, be an inorganic acid such as sulfuric acid, 11, nitric acid or the like, an organic acid such as methanesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid or difluoromethanesulfonic acid; Such as Lewis acid, acid type ion exchange resin and the like. These acid catalysts may be used singly or in combination of two or more. Among the preferred catalysts are, for example, sulfuric acid. The amount of the acid catalyst used is 〇 to 50 mol% relative to dipentaerythritol i mol, preferably 〇. 1 to 2 mol%. In the dehydration condensation reflection of diterpene terpene alcohol with acrylic acid, (meth) propyl fosphate is used in the range of 1 to 2 Torr with respect to dipentaerythritol U, preferably 1 to 10 moles. The reaction time in the dehydration condensation reaction may be in the range of 1 to 24 hours, and the reaction temperature may be in the range of 6 G to 15 (rc), but it is preferably 75 to 12 in terms of shortening of the reaction time and inhibition of polymerization ( The rc is carried out, preferably at a temperature of from 1 Torr to 12 ° C. The reaction solvent in the dehydration condensation reaction is preferably an azeotropic solvent capable of distilling off the water formed in the reaction. The azeotropic solvent herein preferably has The boiling point of 60 to _130C, which can be azeotroped with water and can be easily separated from water. Specifically, it is preferably a non-reactive organic solvent such as benzene, toluene, n-hexane, n-heptane or cyclohexane. It is generally used in the form of two or more kinds. It is generally more preferably toluene. The amount thereof is any, but is preferably from 10 to 70% by mass based on the reaction mixture. (Meth)acrylic acid which is commercially available as a raw material is generally used. A polymerization inhibitor such as a 4-methoxy group is added, but a polymerization inhibitor may be newly added during the reaction. Examples of such a polymerization inhibitor include hydroquinone, 4-methoxyphenol, and 2, 4-di. Mercapto-6-tert-butylphenol, 3-hydroxysulfonate, pair Benzophenone, 2, 5-dihydroxy-p-benzophenone, phenothiazine, etc. Alternatively, chlorinated ketone can be used. The amount used is 〇. 〇1 to 1 by mass relative to the reaction mixture. The amine ester (meth) acrylate compound (A) of the present invention can be obtained by making (I) the following (i), (ii) or (iii), (i) selected from dipentaerythritol tris (A) At least two of the group consisting of acrylate and dipentaerythritol tetrakis(meth)acrylate and dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate and having a hydroxyl group of 80 to 120 mg KOH/g dipentaerythritol poly(meth) acrylate mixture (a) (hereinafter referred to as the mixture (〇; 322127 15 201105694 (ii) both the mixture (a) and glycerin; or (iii) the mixture ( a), glycerin and C2 to C5 aliphatic (2 to 4) alcohol (mercapto) acrylate (hereinafter also referred to as (I) component), and (II) comprising a diisocyanate compound The polyisocyanate compound (b) is obtained by the reaction of the polyisocyanate compound (b). The polyisocyanate compound (b) used in the production of the product (A) may be used as long as it contains two or more compounds having an isocyanate group in one molecule. However, in the present invention, it is necessary to contain a diisocyanate compound. The polyisocyanate compound (b) is preferably a diisocyanate compound alone or a combination of a diisocyanate compound and another polyisocyanate. When used in combination, a diisocyanate compound and a diisocyanate compound are preferably used in combination. The polyisocyanate compound which can be used in the present invention. (b) Examples thereof include an aliphatic polyisocyanate compound, an aromatic polyisocyanate compound, an alicyclic polyisocyanate, or a trivalent or polyvalent compound polyisocyanate or allocyanate. Type polyisocyanate, etc. The trivalent or polyvalent compound means a compound in which three isocyanate groups form one or two or more isocyanate ring structures. The polyisocyanate compound (b) used in the present invention may be a diisocyanate compound alone or a combination of a diisocyanate compound and another polyisocyanate compound as described above. Further, when the diisocyanate compound is used in combination with other polyisocyanate compounds, preferably when the diisocyanate compound and the triisocyanate compound are used together, either of them may be 322127 16 201105694 The type, in addition, can also be plural. Generally, it should be a class. Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate (1,6-hexamethylene diisocyanate), isophorone diisocyanate, hydrogenated indanyl diisocyanate, hydrogenated diphenylene diisocyanate, and hydrogenation. Diphenylmethane diisocyanate, 1,3-diisocyanatocyclohexane, hydrazine, 4-diisocyanatocyclohexane, dicyclohexyldecane _4,4,-diisocyanate, hydrazine, 4 1,4-tetradecyl diisocyanate, 1,12-dodedecyl diisocyanate, 2,2,4-didecylhexamethylene diisocyanate, 2,4,4-tridecyl hexamethylene Iso-cyanohydrazide, monomethylcyclohexanyl diisocyanate, 2,2,4-trimethylcyclohexane diisocyanate, 2,4,4-trimethylcyclohexane diisocyanate, 4, 4_ methylene bis(cyclohexyl isocyanate), diazonic acid diisocyanate, norbornane (dib〇rnane) diisocyanate, bicycloheptane triisocyanate, hexamethylene diisocyanate, etc. A C12 aliphatic di or triisocyanate compound or the like. The aromatic polyisocyanate compound may, for example, be fluorenyl diisocyanate®, monomethyl diisocyanate, diphenyl sulfonium diisocyanate, 1,5-naphthalene diisocyanate, benzidine diisocyanate or hydrazine. 1 to 2 phenylene rings, such as phenyl diisocyanate, 1,6-phenylene diisocyanate, 3-tetradecyldiphenyl diisocyanate, 4,4-mercaptodiphenylene diisocyanate, etc. Or a C6 to C13 aromatic diisocyanate of a naphthalene ring. Among the above-mentioned isocyanates (b), in the present invention, it is preferred to use a diisocyanate compound alone or a combination of a diisocyanate compound and a triisocyanate compound. The diisocyanate compound and other polyisocyanate compounds, preferably 322127 17 201105694 diisocyanate from the compound (four) ratio relative to the diisocyanide compound 1 molar, other polyisocyanate compound (preferably triisoaza) The acid vinegar compound) is preferably from 0 to 10 moles, more preferably from 0 to 5 moles, and most preferably from about 0 to about 3 moles. Further, among the diisocyanate compounds, an aliphatic diisocyanate is preferable, and a C4 to C12 aliphatic diisocyanate is particularly preferable. The ruthenium is preferably hexamethylene diisocyanate, and the diisocyanate compound is preferably hexamethylene diisocyanate. The ratio of use of the oxime isocyanate compound (b) relative to the mixture (a) is relative to the active hydrogen group i equivalent in the mixture (a) (the aforementioned dipentaerythritol poly(indenyl) acrylic brewing mixture (a)) Isochloric acid equivalents = generally in the range of from 0.1 to 50 equivalents, preferably in the range of from 1 to 1 equivalent. When the glycerin is reacted, the glycerol is generally in the range of 〇·01 to 10 equivalents based on the active hydrogen hydrazine equivalent in the poly(meth)acrylic acid vinegar mixture (a)). Good range 1 1 to 1 equivalent range. Further, the active hydrogen group in the mixture (a) means that the hydrogen atom in the hydroxyl group and the active hydrogen group in the (meth) acrylate of the C2 to C5 aliphatic poly(2 to 4) alcohol also mean a hydrogen atom in a hydroxyl group in each compound. Further, in the present invention, the term "hydroxy equivalent" is used, but it can be used in the same meaning as the active hydrogen group equivalent. Further, the ratio of use of the polyisocyanate compound (b) to the mixture (a) 1 mole is based on the hydroxyl equivalent of the mixture (a) and polyisocyanate, the isocyanate equivalent in the compound (6), and glycerin. And the use of C2sC5 aliphatic polyterpene (2 to 4) alcohol (mercapto) acrylate in combination with the presence or absence of change, 322127 18 201105694 is difficult to generalize, but should be relative to the mixture (a) 1 mole, in 〇 3 In the range of up to about 1 m, preferably in the range of about 0.3 to about 9 m, more preferably in the range of 0.33 to 0.8 m using the polyisoester compound (b) . For example, when the component (I) is (i) the mixture (a) is used alone, the polyisocyanate compound (b) 〇3i 〇. 7 moles or more is preferably used with respect to the mixture (a) l mole. 〇. 33 to 0. 6 m or so. Further, when the component (I) is (ii) or (iii) (when the mixture (a) is used in combination with glycerin), the polyisocyanate compound (b) is more preferably added depending on the molar number of glycerin to be used in combination. Usage amount. The amount of the polyisocyanate compound (b) to be added is preferably in the range of from about half to about one times the number of moles of glycerin. For example, the polyisocyanate compound (b) is preferably added in an amount of from 1 mole to about 3 moles per mole of the mixture (a) to about 3 moles to 2 moles of glycerin. The amount of the diisocyanate compound alone or in combination of the diisocyanate compound and the triisocyanate compound is from about 3 to about 3 moles, more preferably from 0 to 莫. 2 moles relative to the mixture (a) l mole. The ratio of the ears. Further, when the (meth)propionate of the C2 to C5 aliphatic polybasic (2 to 4) alcohol has a carboxyl group, it is preferred to increase the number of NCO equivalents in an equivalent amount corresponding to the number of equivalents of the radical. Isocyanate compound (b). In general, it is preferred that the total number of equivalents of the active hydrogen groups of the components in the mixture (a) is the same as the number of equivalents of the NCO of the polyisocyanate compound (b) to be reacted or the number of equivalents of the NCO is within 0.1%. In the excess amount, the reaction is 0. In the present specification, 1 mole of the mixture (a) is the content ratio (molar number) of each component in the mixture (a) of 19 322127 201105694 with respect to the mixture. The sum of the total amount of (a) (the sum of the molar numbers of the respective components) multiplied by the respective molecular weights is defined as the value at the molecular weight of the mixture (a). Further, the (meth)propionate of the C2 to C5 aliphatic polybasic (2 to 4) alcohol used in (I) may be, for example, a C2 to C5 aliphatic such as ethylene glycol, propylene glycol or pentaerythritol. A acrylate obtained by reacting a polyhydric (2 to 4) alcohol with (meth)acrylic acid. The (meth) acrylate is preferably contained in an amount of 30 to 100% by mass, preferably 5 to 1% by mass, based on the total amount of the (meth) acrylate. (The remainder is an acrylate of a C2 to C5 aliphatic poly (2 to 4) alcohol having no hydroxyl group). Preferred are, for example, hydroxyethyl (meth)acrylate and poly(2 to 4) (meth) acrylate of pentaerythritol (preferably pentaerythritol di or tri(indenyl) acrylate and pentaerythritol tetra(methyl). A mixture of acrylates, more preferably a hydroxyethyl acrylate or a mixture of pentaerythritol tri- and tetra-acrylates (for example, a mixing ratio (quality) 2. 4 = 1: 〇. 〇1 to 1' is preferred 1: i To 〇. 6). The reaction system comprising the component (I) of the mixture (a) and the (I) polyisocyanate (b) can be carried out in the same manner as in the general amine esterification reaction. The reaction can also be carried out in the presence of an inert organic solvent such as a ketone solvent such as methyl ethyl ketone or a catalyst as needed. The reaction temperature is usually from 30 to 150. The range of (: is preferably in the range of 50 to 1 〇〇 ° C. The end of the reaction is carried out by reacting residual isocyanate groups (NCO) with excess n-butylamine and counter-titrating with 1 N hydrochloric acid. The content of the residual isocyanate group (NCO) is 5% or less, preferably 5% or less, based on the content of the isocyanate group (NC0) of the polyisocyanate (b) used as a raw material, and the residual isocyanate group 322127 20 201105694 (NC0) content is preferably 0.5% or less. 0. 1% or less is used as the end point. The catalyst may be added for the purpose of shortening the reaction time. Any one of the alkaline catalyst and the acidic catalyst may be used as the catalyst. An amine such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine or ammonia; a phosphine such as tributylphosphine or triphenylphosphine; and an acid catalyst such as copper naphthenate, Metal alkoxides such as cobalt naphthenate, naphthenic acid, tributoxy aluminum, tetrabutoxy titanium, tetrabutoxy zirconium, etc., Lewis acid such as aluminum chloride, tin 2-ethylhexanecarboxylate , octyl tin laurate, dibutyl tin dilaurate, octyl diacetate The tin compound is preferably an acid catalyst of a tin compound, more preferably dibutyltin dilaurate. The amount of the catalyst added is 100 parts by mass relative to the polyisocyanate S compound (b), generally 0. 1 part by mass or more and 1 part by mass or less. Further, in the reaction, in order to prevent polymerization in the reaction, a polymerization inhibitor (for example, 4-decyloxyphenol, 2,4-didecyl-6-t-butyl group) is preferably used. 01质量质量。 The mass of the reaction mixture is 0. 01 mass % or more of 1% by mass or less, preferably 0.05% by mass or more and 0.5% by mass or less. The amine acetonate (mercapto) acrylic acid vinegar compound (A) obtained as described above is not a single amine ester compound, and It is obtained in the form of a mixture of amine ester compounds having a different degree of polymerization, such as a polymer compound, etc., especially in glycerin, or a further C2 to C5 aliphatic polybasic (2 to 4) alcohol (曱21 322127 201105694 The coexistence of propylene and coffee, so that the aforementioned poly (meth) propylene ride (4) (4) A product obtained by reacting with a polyisocyanate compound (6), which is a mixture of complex polycondensates (amine acetonate), the obtained amine acetonate (meth) acrylate The viscosity (10) C) of the vinegar compound (1) is about 5 to 40 Pa·s, preferably about 1 to 38 Pa·s, more preferably about 12 to 38 Pa·s, and most preferably about 14 to 35 pa.s. Further, in the best case, when the viscosity is l5 Pa · s or more, the curling property is less, the viscosity is Π Pa. s or more, the curling property is less, and the viscosity is ΐ 8ρ & s or more, the curling property is the least. Further, the weight average molecular weight (MW) is 3, _ to 5 〇, _ or so, preferably about 4,000 to 35,000, more preferably 4, 5 〇〇 to buckle, and (10) 〇 around 'best 5 , 000 to 35, 0〇〇 or so. In order to obtain a hardened film with less distortion, the weight average molecular weight is 7, from about 50,000 to about 50,000, preferably from about 7,000 to about 35,000. The number average molecular weight is about 1400 to 2500, preferably about 5 to 2300, more preferably about 1600 to 2300, the best is about 17 to 2300, and the best is about 1700 to 2100. The amine ester (mercapto) acrylate compound (A) is more preferable in that the weight average molecular weight is about 4,500 to 35,000 'the number average molecular weight is about 2,300, and the viscosity is 60. The enthalpy is about 5 to 40 Pa.s. Further, one of the best aspects is a weight average molecular weight of about 7,000 to 35,000, a number average molecular weight of about 1,700 to 2,300, and a viscosity (6 〇. 〇 is about 12 to 35 Pa·s. The amine ester of the present invention ( A mercapto acrylate compound, based on the ratio calculated from the area ratio of Hplc 322127 22 201105694 and GPC (gel permeation chromatography), generally comprising an amine esterified (meth) acrylate (amine) (Meth) acrylate) is about 6 to 90%, preferably about 60 to 85%, and the remainder is about 1 to 4%. Preferably, about 15 to 40% is unesterified. Methyl) propenyl ester (unreacted dipentaerythritol hexa(meth) acrylate derived from raw materials and pentaerythritol multi-quantity without esterification (more than three or more). Glycerin and C2 are not obtained. C5 aliphatic multi-component (2 to 4) alcohol (royl) acrylate coexists, and When the above poly(meth)acrylate mixture (&) is reacted with 2 lenore polyisocyanate compound (b) (diisocyanate compound), it is an amine ester (meth) acrylate represented by the following formula (1). Compound (eight

In the formula, X represents an isocyanate residue, η represents an integer of 0 to i〇〇, and A, β and γ represent an organic group represented by the following formula (2). -ΟΗ, CH,0--oh2c-c-ch2och2c!; —oh2c ch2o- I ch2o—— _(icH=CH2)af~H)b *B)c (2) (1) Y represents the general formula ( 2) In the case of the organic group shown, x is an isocyanate residue, a, b and c are positive integers, a + b + c = 4, 丨 is ^ 〇 gb^3 and 0 'Y is a divalent base, (2) When Α represents an organic group represented by the formula (2) or Β is present at the terminal, 23 322127 201105694 is an integer of isocyanate residue, and a + b == 5, ^ t lies When the terminal is other than the terminal, C is G, X is an isocyanate (tetra) residue, an integer of & and =, and a + b = 4. However, when β exists outside the end, theoretically, 寺 is the same as γ, and 寺 is the same as γ. In the present specification, it is simplistic, and is expressed as described above. Therefore, when the organic group represented by the formula (2) is in the form of the organic group represented by the formula (2) and the oxime is present outside the terminal, the formula (2) is a divalent group, and Α represents the formula (2). When the organic group and B are present at the terminal, respectively, the formula (2) is a monovalent group. In the case of the above (2) (A represents an organic group represented by the formula (2) or when β is present at the terminal), the formula (2) can be represented by the following formula (2a). -oh2c -oh2c—i—ch2och2c!:· CH20-

-1 Ο-(A

CH=CH 2 hr ch2o· '°h2c ch2o— fH)丨(2a) where 'a' and b are positive integers, a, +b' =5, l$a, and 0$b' $4 The resin composition of the present invention comprises the amine ester (meth) acrylate compound (A) of the present invention and a photopolymerization initiator (C), and may optionally contain (meth) acrylate (β), Hardening accelerator (D), diluent (e), and other ingredients. Other ingredients include, for example, a leveling agent, an antifoaming agent, an ultraviolet ray 322127 201105694 2 absorption etch, a light stabilizer, an antioxidant, a polymerization inhibitor, a crosslinking agent, and the like. The resin composition of the present invention is a photosensitive resin composition which can be cured by an energy ray such as ultraviolet rays. Further, in order to easily form a film form such as a hard coat layer, the resin composition of the present invention preferably contains an organic solvent as the diluent (E). In the resin composition of the present invention, the content of the amine ester (meth) acrylate compound (A) of the present invention is a solid content of the resin composition of the present invention. When it is 100% by mass, it is generally 5 to 97% by mass, preferably 20 to 8% by mass. 'Also, depending on the case, it is preferably about 40 to 95% by mass, more preferably about 5 to 95% by mass. It is about 7 to 95% by mass. Further, the content of the (meth) acrylate compound (A) is usually from 5 to 97% by mass, preferably from about 95% by mass, more preferably about 4%, based on the total amount of the resin composition of the present invention. It is about 95% by mass, and most preferably it is about 95%. (Meth) acrylate which can be used in the present invention (magic), for example, a (meth) acrylate compound other than the amide amine (meth) acrylate compound (A), for example, mono (methyl) Acrylate (acryloyl acrylate is one acrylate) or polyacrylate (bifunctional (fluorenyl) acrylate or trifunctional or higher (meth) acrylate: propylene fluorenyl is 2 or more acrylates And the like. The polyacrylate further comprises a polyester (meth) acrylate or an amine ester (meth) acrylate oligomer (except for the aforementioned amine ester (mercapto) acrylate compound (A)), A polyester (meth) acrylate oligomer or an epoxy (meth) acrylate oligomer, etc. These may be used alone or in combination of two or more. 25 322127 201105694 In the present invention, it is preferred to have ( Methyl)propenyl fluorenyl 2 to 6 as many (meth) acrylic acid vinegar compounds. Preferred poly(indenyl) acrylic acid hydrazine compounds are, for example, C1 to C12 aliphatic diols (f groups) Acrylic vinegar or dipentaerythritol (3 to 6) (mercapto) C For example, q to C12 aliphatic diol diacrylate or dipentaerythritol (3 to 6) propionic acid vinegar. C1 to C12 aliphatic diol diacrylate is preferably C1 to c 6 fat. Group diol diacrylic acid vinegar. When obtaining a film having flexibility, it is preferably a C1 to C12 aliphatic diol diacrylate. When a hardened product having a high hardness is desired, it is preferably dipentaerythritol (3 to 6). Further, in the present invention, the expression "(indenyl) acrylate" or the like means that the acrylic acid may have a methyl group, for example, "(meth)acrylic acid vinegar" The meaning of acrylate or f-based acrylate. Also, the expressions "more (3 to 6)" or "more (2 to 4)" mean "more" to "3 to 6" or "2" Examples of the mono(meth)acrylate include acryloyl morpholine; 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like (hydroxyl group). Acrylate; cyclohexane-hydrazine, 4-dimethanol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, Methyl) dicyclopentanyl acrylate, dicyclopentenyl (mercapto) acrylate, (f-based) propylene-e-pentenyloxyethyl ester, aliphatic (mercapto) acrylate; benzene (meth) acrylate Oxyethyl ester, phenyl (poly)ethoxy (meth)acrylate, 4-cumylphenoxyethyl (meth)acrylate, tribromophenyloxyethyl (meth)acrylate 322127 26 201105694 vinegar, (fluorenyl) phenylthioethyl acrylate, (meth)acrylic acid 2_hydroxy_3_phenoxypropyl ester, streptophenol (meth)acrylic acid (poly)ethoxylate, phenyl phenylene epoxy An aromatic (meth)acrylic acid vinegar such as a (meth)acrylic acid vinegar. The bifunctional (meth) acrylate may, for example, be 14 _ propyl or u-hexane diol ((3) two dilute acid awake, (A Acetate, tricycloanthracene dimethanol (meth) acrylate acetonate, bisphenol A — (mercapto) acrylate (poly) ethoxylate, bisphenol plant di(meth)acrylic acid (poly) Propoxylate, bisphenol F di(meth)acrylic acid (poly)ethoxylate, ethylene glycol di(meth)acrylic acid g曰, (poly)ethylene glycol di(meth)acrylate Di(meth)acrylic acid vinegar of ε-caprolactone adduct of glutamic acid neopentyl glycol vinegar (for example, Nippon Kayaku Co., Ltd., KAYARAD ΗΧ-220, ΗΧ-620, etc.) An epoxy acrylate such as bisphenol quinone di-epoxy acrylate or the like. Examples of the polyfunctional (meth) acrylate of 3 g or more include bis(trihydroxydecylpropane)tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trishydroxyl. Octyl octane tri(meth) acrylate, trimethylolpropane di(meth) acrylate (poly) ethoxylate, trimethylolpropane tris(methyl) propane acid (poly) propoxylate, three Poly(meth)acrylates of methylol groups such as methylolpropane tris(meth)acrylic acid (poly)ethoxy (poly)propoxylate; pentaerythritol di(meth)acrylate, pentaerythritol tetra(methyl) Acrylic (poly)ethoxylate, pentaerythritol tetra(meth)acrylic acid (poly)propoxylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylic acid Poly(indenyl) acrylates such as erythothoyl esters such as esters and dipentaerythritol hexa(indenyl) acrylate; tris[(indenyl) propylene oxyethyl]trimeric isocyanate and caprolactone modification Three [(indenyl) propylene oxime 2127 27 201105694 ethyl] two Isocyanate (X Yue multi-yl) acrylate, isocyanuric Sa 0 (poly) ester (meth) acrylates such as for example (polyester) diol bis (Yue-yl) acrylate. The (poly) ester diol can be obtained by reacting a diol compound with a dibasic acid or an anhydride thereof. Examples of the diol compound include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, (poly)ethylene glycol, and (poly)propylene glycol. ; 1,4-butanediol, iota, 6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-mercapto-1,8-octanediol, 3-mercapto a linear or branched alkyl diol such as -1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol An alicyclic alkyl glycol such as cyclohexane_ι, 4-didecyl alcohol; bisphenol A (poly)ethoxy glycol, or bisphenol A (poly) propoxy glycol or the like. The dibasic acid or an acid anhydride thereof may, for example, be succinic acid, adipic acid, sebacic acid, polyacid, meta-decanoic acid, acid donating, diacid or acid liver. The month 'J amide (mercapto) acrylate oligomer may, for example, be a reaction product of a diolation compound (also including the above polyester diol) and an organic polyisocyanate to form a hydroxyl group-containing (fluorenyl group). An amine ester (mercapto) acrylate oligomer obtained by acrylate (except for the aforementioned amine ester (meth) acrylate (A)). The diol compound may, for example, be a (poly)ethylene glycol (for example, ethylene glycol, diethylene glycol, triethylene glycol, or a higher degree of polymerization of polyethylene glycol) or (poly)propylene glycol (for example, propylene glycol, two Propylene glycol, tripropylene glycol, or a higher degree of polymerization of propylene glycol), 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 28 322127 201105694 1,9- Decylene glycol, 2_methyl one! ,8-octanediol, 3-methyl-pentanediol, 2,4-diethyl-hydrazine, 5-pentanediol, 2-butyl-2-ethyl-ethyl, 3-propylene glycol, cyclohexane Alkane 1,4-methanol, etc. ci to C12 aliphatic diol or poly(C2 to C4 alkylene) diol; bisphenol A (poly) ethoxy diol or bisphenol a (poly) propoxy- A double 19A (poly) C2 i C391-based diol such as an alcohol; or a polyester diol or the like which is a reaction product of the diol compound with a dibasic acid or an anhydride thereof. Further, examples of the above-mentioned dicarboxylic acid or an acid anhydride thereof include succinic acid, adipic acid, sebacic acid, dimer acid, meta-antimonic acid, p-citric acid, citric acid or the like. The organic polyisocyanate used in the synthesis of the above amine ester (mercapto) acrylate merging agent may, for example, be tetradecyl diisocyanate, hexamethylene diisocyanate or 2, 2, 4-tridecyl hexa Chain-like saturated hydrocarbon isocyanate such as mercapto diisocyanate or 2,4,4-didecylhexamethylene diisocyanate; isophorone diisocyanate, norbornane diisocyanate, dicyclohexyldecane diisocyanate, Aa a cyclic saturated hydrocarbon isocyanate such as bis(4-cyclohexyl isocyanate), hydrogenated diphenyldecane diisocyanate, hydrogenated dimethyl diisocyanate or hydrogenated toluene diisocyanate; 2, 4-nonyl diisocyanate, 1,3- Diphenylene diisocyanate, 4-extended diisocyanate, 3,3,-dimethylbiphenyl-4,4,-diisocyanate, 6-isopropyl 4,3-phenyl diisocyanate, 1, An aromatic polyisocyanate such as 5-naphthalene diisocyanate. The above (poly)ester (fluorenyl) acrylate oligomer may, for example, be a (poly) vinegar (mercapto) acrylate obtained by reacting the above-mentioned poly(mono) alcohol with (mercapto) acrylic acid g. Oligomers, etc. Further, the epoxy group (meth) acrylate oligopolymer is epoxide (meth) acrylate 29 322127 201105694 vinegar oligomer obtained by reacting an epoxy resin with (mercapto) acryl. The epoxy resin used herein is preferably an epoxy resin having a plurality of epoxy groups. In the resin composition of the present invention, the amount of the above (f group)__(8) is such that when the solid content of the resin composite of the present invention is classified into (10), the ratio to the above is generally 〇% by mass or more. The amount of 94f is preferably from 0 to 60% by mass, and is preferably from 5% by mass, more preferably from 1% to 60% by mass, as long as it is greater than zero. Also, depending on the situation, it is also 80% by mass. 1 thief, the content of the (meth) acrylate (B) relative to the resin composition of the present invention is generally from 〇 to 50% by mass, preferably from about 〇 to about 4% by mass, more preferably from 0 to 30% by mass. % left 纟, when used, as long as it is greater than zero, preferably from 3 to 50 mass, more preferably from 5 to 4% by mass, most preferably from 5 to 卯%, in the photopolymerization used in the resin composition of the present invention The starting agent (c) may, for example, be stupid, benzoin decyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether or the like; 2,2-diethoxyphenyl acetamidine, 1,1-dioxabenzene, 2-hydroxy-2-indolyl propan-1-one, diethoxyethyl benzene, hydroxy Cyclohexyl phenyl ketone, methyl 1 [4-(indolyl) benzyl] 2 - phenanthropropan-1-one, etc.; 2-ethyl hydrazine, 2-tert-butyl蒽, 2-gas 蒽醌, 2-pentyl 蒽酉 蒽 and other 蒽 relatives; 2, 4-diethyl thia fluorenone, 2-isopropyl thioxanthone, 2 ~ thiazepine, etc. a thioxanthone (such as i〇xanth〇ne); a ketal such as a benzoyl hydrazide; a benzoquinone dimethyl ketal; Dibenzophenone, 4-benzoquinone-4'-methyldiphenyl sulfide, 4,4'-bis-decylaminodibenzophenone, etc. 30 322127 201105694 Benzophenone, 2, 4 a phosphine oxide such as 6-trimethylbenzimidyldiphenylphosphine oxide or bis(2,4,6-dimethylbasinyl)phenylphosphine oxide. Further, specifically, IrgacUreRTM 184 (1-hydroxycyclohexyl phenyl ketone) and Irgacure 9 〇 7 (2-mercapto-1-(4-(sulfonylthio)phenyl) manufactured by Ciba Specialty Chemicals Co., Ltd. are readily available from the market. _2-morpholinopropane- ketone), Lucirin TP0 (2,4,6-trimethylbenzimidyldiphenylphosphine oxide) manufactured by BASF Corporation. Further, these may be used alone or in combination of two or more. Among these, it is preferably a photopolymerization initiator belonging to the class of acetophenone benzene, more preferably 1-cyclohexylphenyl phenyl group (1 is 3 〇 1 『61{, in the resin composition of the present invention. The content of the photopolymerization initiator (c) is such that when the solid content of the resin composition of the present invention is 1% by mass, it is 0.1% by mass or more and 10% by mass or less, preferably 1% by mass or more. Further, the content of the photopolymerization initiator (100% by mass relative to the solid content of the resin composition of the present invention may be about 2 to 12% by mass. In this case, it is preferably 0. 5 to 10% by mass, more preferably about j to 1% by mass, most preferably about 2 to 8% by mass. Further, the above photopolymerization initiator (C) may be used together with a hardening accelerator (^ The hardening accelerator (D) which can be used in combination may, for example, be triethanolamine, diethanolamine, N-decyldiethanolamine, benzamic acid 2-mercaptoamine ethyl acetonate, dimethylaminoethyl benzene benzene, 4-di a hydrogen donor such as a mercaptoamine-based isoamyl formate, an amine such as EPA, or a hydrogen donor such as 2-hydrothiobenzothiazole. The use amount of such a hardening accelerator is such that the present invention When the solid content of the fat composition is 1% by mass, it is 5% by mass or more and 5% by mass or less. These may be used singly or in combination of two or more. 322127 31 201105694 The resin composition of the present invention may be used as needed The diluent (E) is used. The diluent (E) is a solvent which is a liquid at normal temperature (20 ° C). Generally, an organic solvent is used. For example, 7*-butyrolactone, T-valerolactone, and 7-hexyl Lactones such as lactone, 7-heptanolactone, α-ethinyl-r-butyrolactone, ε-caprolactone, etc.; dioxane, 1,2-dimethoxy oxime, Diethylene glycol dimercapto, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monodecyl ether, propylene glycol monoethyl ether, triethylene glycol didecyl ether, triethyl Ethers such as diol diethyl ether, tetraethylene glycol didecyl ether, tetraethylene glycol diethyl ether; carbonates such as ethyl carbonate and propylene carbonate: mercaptoethyl ketone (2— Ketones such as butanone), mercaptoisobutyl ketone 'cyclohexanone, acetophenone benzene; phenol, cresol, xylenol · #龄类, ethyl acetate, butyl acetate, ethyl acetate, ethyl acetate Fibril acetate, Base cellosolve acetate, carbitol acetate, butyl carbitol acetate vinegar, propylene glycol monomethyl ether acetate and other esters; toluene, xylene, diethylbenzene, % hexane and other hydrocarbons ; halogenated hydrocarbons such as trichloroethane, tetrachloroethane, and monogas; petroleum petroleum solvents such as petroleum ether and petroleum brain; fluorine alcohols such as 2H, 3H_tetrafluoropropanol; perfluorobutyl methyl ether; Hydrofluoroethers such as perfluorobutyl ethyl ether; alcohols such as methanol, ethanol, isopropanol, and n-propanol; * dipropanol (diacet〇ne alc〇h) having properties of both ketone and alcohol 〇l), etc. It may be used singly or in combination of two or more. It is more preferable to use an ester solvent such as two ethyl esters (preferably as an acetate of 3 alcohols) or a ketone solvent. (7) to (3) aliphatic networks. ^ Λ only 巧 & yfcy J and is 0 to 80 士 士 · 左右 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ (4) The content of (4) is 322127 32 201105694. When the solid content of the resin composition of the present invention is divided into 100% by mass, the content of the diluent (E) is about 0 to 300% by mass, preferably 〇 2% by mass, more preferably from about 150 to about 150% by mass. In the present specification, the content of the component of the composition, for example, as described above, the content of "0 to 90% by mass" including 〇 means that the component is not contained, or is greater than 0 and 90% by mass or less. The scope is included. Further, the resin composition of the present invention may contain, as needed, a coating agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor, a crosslinking agent or the like as an additive other than the above. By including these, the functionality of the purpose can be separately provided. The coating agent may, for example, be a fluorine-based compound, a polyfluorene-based compound or an acrylic acid-based compound, and examples of the ultraviolet absorber include a benzotris-based compound, a benzophenone-based compound, and a tri-farming compound. The anti-oxidation agent such as a hindered amine compound or a benzoate compound may, for example, be a phenol compound or the like. The polymerization inhibitor may, for example, beformam, methylhydroquinone or hydroquinone. The crosslinking agent may, for example, be a pro-acid hydrazine or a melamine compound. Cardioisocyanide t is one of the preferred resin compositions of the present invention comprising the amine compound of the present invention = acid ester compound (A), and photopolymerization initiator (c) and is coated with 1, propylene oxime The resin composition of at least one of the vinegar (8) or the diluent (8) preferably has a solid content of 100, as exemplified by the following mass %, and more specifically, the present invention. The composition ratio is the ratio of the resin to it. 5至12质量%, 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 (meth)propionate (B) 0 to 50% by mass, and diluent (E) 0 to 300% by mass, and the diluent (E) is an organic solvent. (ii) The resin composition according to the above (i), which contains the amine ester (fluorenyl) acrylate compound (A) in an amount of 40 to 95% by mass. (iii) The resin composition as described in (i) or (ii) above, wherein the organic solvent containing 5 to 40% by mass of (meth) acrylate (B) or 5 to 40% by mass of the diluent (E) At least either of %. (A) The resin composition according to any one of the above-mentioned (A), wherein the amine oxime (meth) acrylate compound (A) is the above (!) to (4), (5), (10), the amine (meth) bisacetoate compound (A) according to any one of (10) to (10) and (19), or any one of the above (5), (7) or (11) The hydroxy ester (meth) acrylate compound (manufactured by the above-mentioned (1) to (5), the photopolymerization initiator (C) It is a photopolymerization initiator belonging to the class of acetophenone benzene. (vi) The resin composition as described in any one of the above (1) to (v), in which the (meth) propylene (4) (8) is a C1 to C12 aliphatic Diol bis (methyl vinegar or dipentaerythritol (3 to 6) (methyl) acetoacetate. ^11) Resin composition as described in any one of the above (1) to (V1), Fuzhong The diluent (E) is a ketone solvent. 树脂 The resin composition of the present invention is particularly useful as a hard coat resin composition (hard coater), and can be used as a gas system 322127 34 201105694 which will be described later. Components, A material for molding such as a sub-part. The resin composition of the present invention can be obtained by mixing the component (A) and the component (8), the component (8), the component (8), and other components in an arbitrary order. The hard coat layer of the present invention can be obtained by applying the resin composition of the present invention to a green substrate and drying it, and forming a cured film on the formed film irradiation line. More specifically By using a bar coating, it is possible to make the dry thickness as 0.1 犋乂 300 // in or less, generally 〇. 1 to m or less, and more preferably 1 丨 "1« above 20//m In the following manner, the above-mentioned tree test product is applied as needed, and then irradiated with an ultraviolet ray film. Λ The film thickness after the aging is used, and the film thickness after hardening* 〇阳乂上30〇am The loose production and the right 'should be about 1 Μ m or more and 250 μm or less. When the coating film is formed on the base 5, the film thickness after hardening is generally 〇· Above JUem, the official hair is τ or more, 2〇# m or less, more preferably 10//ΙΠ, most preferably the following. gt “The cows such as polyester, polypropylene women Polyethylene, polyacrylic acid%, polycarbonate gt-1,3-diethylcellulose, polyether oxime, cycloolefin polymer for use in 0. The film system can also be provided with a pattern or easy to laminate, For surface treatment by corona treatment, etc., the coating method of the above resin composition may be, for example, bar coater coating, 'chopper coating, air knife coating, gravure coating, reverse Gravure coating, micro gravure coating · 彳古 ^ 1 printing 'micro-reverse gravure coater coating, die coater coating, dipping 35 322127 201105694 ulcer coating, spin coating, spray coating and so on. In order to harden, ultraviolet rays are irradiated, but an electron beam or the like may also be used. When the ultraviolet light is hardened, the light source can be used and has an ultraviolet ray irradiation device such as an air _ _, an eight-page xenon lamp, a high-pressure mercury lamp, a metal i-lamp, and the like, and the configuration of the amount of light, (4), and the like. When a high-pressure mercury lamp is used, it is preferably hardened at a transport speed of 5 to 6 Gm/min with respect to a lamp having an energy of 8 Torr. Further, in the case of hardening by electron beam, it is preferable to use an electron beam accelerating device having energy up to the other (4), and in this case, the photopolymerization initiator (6) may not be used. The cured film of the resin composition of the present invention can be suitably used as a material for a display device because it has adhesion to a plaque substrate and hardness, and has moderate flexibility. For example, an LCD, an EL, a f-side projection ((10)^ _ecti〇n) display, a material for a color grading sheet used for electronic paper, etc., a thin display element used for partitioning, electronic paper, etc., an LCD, a FED A spacer (used as a stencil) used for (SED) or the like, or a solid-state imaging device such as a digital camera. The cured product of the resin composition of the present invention is particularly suitable as a resin for a solid-state imaging device such as a liquid crystal display device or a digital camera, and is widely used as a color light-emitting sheet. The color light film has a colored pixel of a plurality of colors patterned by a cured product of the silk tree wax composition of the present invention prepared by the first two methods, or a black matrix or a light matrix: In the display device of the invention, a liquid crystal display device is used as an example of a laminated backlight, a polarizing film, a display electrode, a liquid crystal, an alignment iridium, a through electrode, a color light film common polarizing film using the photosensitive resin composition of the present invention, and the like. Made of the structure. Further, taking a solid-state imaging device as an example, 322127 36 201105694, for example, by providing a color filter layer using the photosensitive resin composition of the present invention on a wafer on which a transfer electrode and a photodiode are provided, and then laminating micro Made with a lens. Another use of the photosensitive resin composition of the present invention can also be used, for example, in printing inks, paints, adhesives, liquid photoresist inks, and the like. (Examples) Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by the examples. Further, in the examples, the parts represent the parts by mass unless otherwise stated. The abbreviations used in the 'in the embodiment' are as follows. DPETtriA: dipentaerythritol triacrylate DPETtetraA: dipentaerythritol tetraacrylate DPETpentaA: dipentaerythritol pentaacrylate DPEThexaA: dipentaerythritol hexaacrylate and TPETA: hexaerythritol or higher acrylates HPLC: high performance liquid chromatography GPC: Gel Permeation Chromatography Further, HPLC and GPC measurement conditions were as follows. (HPLC measurement conditions)

Device: SHIMADZULC-10AD, SCL-10A, SPD-10A, CTO-10A, DGU-14A Detector: UV 254nm Column: GL Science Inertsil ODS-2 (4.6xl50mm)

Column temperature: 40 ° C Dissolution: acetonitrile / O.lwt% H3P 〇 4 = 60 / 40 37 322127 201105694 Flow rate: 0. 6m 1 / min. Sample injection amount: 2 ν 1 Sample concentration: lwt% ( GPC measurement conditions)

Apparatus: TOSOH HLC-8220 GPC Detector: RI Column: TOSOH TSK-GEL SUPER HZM-N Column temperature: 40 °C Dissolution: THF Flow: 0. 35 ml/min. Sample injection: 5 # 1 The sample concentration is 1 wt% (raw material synthesis example 1) in a reactor equipped with a reflux cooler, a mixer, a thermometer, a temperature regulating device, and a water separator, feeding dipentaerythritol 254.3 g (l.〇m〇 i), acrylic acid 449. 7g (6.2 mol), sulfuric acid 9.81g, chlorinated ketone 1. 〇 3g, toluene 424. 7g 'heat the reactor, while the formation of water and solvent azeotrope, while reacting for 12 hours . After the reaction, the mixture was diluted with 849. 4 g of toluene, neutralized with a 25% aqueous NaOH solution, and washed three times with 600 g of 15% by mass aqueous saline. 9克。 The solvent was decompressed to obtain a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA (hydroxyl: 80mgKOH / g, hydroxyl equivalent (active hydrogen equivalent): 701.4g / Eq) 538. 9g. The ratio of DPETtetraA, DPETpentaA, DPEThexaA and TPETA in the area ratio (%) of high performance liquid chromatography (HPLC) 38 322127 201105694 The ratio is 10: 43 : 37 : 10. Further, the viscosity of the mixture was 6300 mPa·s (25 ° C). _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ And sulfuric acid 9.81g 'chlorinated ketone 0. 99g, 曱 424. 7g, heated reactor, while the formation of water and solvent azeotropic distillation, while reacting for 12 hours. After the reaction, the mixture was diluted with 849. 4 g, diluted with 25% NaOH aqueous solution, and washed three times with 600 g of 15% by mass saline. The solvent was evaporated under reduced pressure to give a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA (hydroxyl valence · 92 mg K0H/g, hydroxy equivalent: 609.9 g/Eq) 525.3 g. The ratio of each component of DPETtetraA, DPETpentaA, DPEThexaA and TPETA in terms of HPLC area ratio (%) was 12:45:36:7. Further, the viscosity of the mixture was 63 〇〇 mPa · s (25 t). ( Raw material synthesis example 3) In a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature regulating device, and a water separator, feeding dipentaerythritol 254.3 g (1〇m〇1), acrylic acid 402. lg (5 6 mol), sulfuric acid 9.81 g, chlorinated ketoxime, 92 g, toluene 424.7 g, and the reactor was heated, and the produced water and the solvent were azeotropically distilled, and reacted for 12 hours. After the reaction, 84. 4 g of toluene was added and diluted, and after neutralizing with a 25% aqueous NaOH solution, it was washed three times with 15 g of 15 g of saline. The solvent was distilled off under reduced pressure to give a mixture of DPETtriA, DPETtetraA, DPHpenta A'DPEThexaA and TPETA (hydroxyl: 12 〇mg 39 322127 201105694 KOH/g, base equivalent: 466.7 g/Eq) 494.9 g. The ratio of each component of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA and TPETA was 3:26:41:24:6 in terms of area ratio (%) of HPLC. Further, the viscosity of the mixture was 6000 mPa·s (25t:). 2克(6. 2g(6) (6. 2g (6. 9 mol), 9.81 g of sulfuric acid, 1.41 g of vaporized ketone, and 42. 7 g of toluene. The reactor was heated while the produced water and the solvent were azeotropically distilled, and reacted for 12 hours. After the reaction, the mixture was diluted with 849. 4 g of toluene, neutralized with a 25% aqueous NaOH solution, and washed three times with 600 g of 15% by mass aqueous saline. The solvent was distilled off under reduced pressure to give a mixture of DPEITtetraA, DPETpentaA, DPEThexaA and TPETA (hydroxyl: 45 mg KOH/g, hydroxyl equivalent: 1246. 9 g/Eq) 590. lg. The ratio of each component of DPETtetraA, DPETpentaA, DPEThexaA and TPETA in terms of area ratio (%) of HPLC was 2:30:56:12. Further, the viscosity of the mixture was 6500 mPa·s (25 ° C). (5. 5g (5) (5. 5g (5) (5. 5g (5) 3 mol), 9.81 g of sulfuric acid, ketone ketone chloride, ggg, and benzene 424. 7 g, the reactor was heated, and the produced water and the solvent were azeotropically distilled, and reacted for 12 hours. After the reaction, the mixture was diluted with 849. 4 g, and after neutralizing with a 25% aqueous NaOH solution, it was washed with 15 g of salt water of 600 g of 3 40 322127 201105694 times. The solvent was decompressed to give a mixture of DPETtriA, DPETtetraA, DPETpenta A'DPEThexaA and TPETA (base price: 140 mg KOH/g, hydroxyl equivalent: 400. 8 g/Eq) 480. lg. The ratio of each component of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA, and TPETA was 4:30:42:19:5 in terms of area ratio (%) of HPLC. Further, the viscosity of the mixture was 5,800 mPa·s (25 ° C). (Example A) (Synthesis Example 1) A mixture of DPETtetraA, DPETpentaA, DPEThexaA, and TPETA obtained in Synthesis Example 1 was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjusting device. Valence: 80 mg KOH/g, hydroxyl equivalent: 701.4 g/Eq) 446.47 g (0.64 mol), 4-nonoxyphenol as a polymerization inhibitor, 0.25 g, dibutyltin dilaurate as an amine esterification reaction catalyst 2525g and stir until uniform, so that the internal temperature is 50 °C. Then, 53. 53g (0.22 moles) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 ° C. After the addition, the reaction was carried out at 80 ° C for 6 hours to obtain the above-mentioned NC0 content. When the concentration is 0.1% or less as the reaction end point, the amine ester acrylate of the present invention is obtained. This system has an average molecular weight (Mw = 4500, Mn = 1500) and a viscosity of 6 Pa.s (60 ° C). Further, after confirming the components of the obtained amine ester acrylate by HPLC and GPC, the content of the amine ester acrylate was 64% (ratio to the total amount), and the acrylate having no amine esterification (unreacted DPEThexaA) The content of the by-produced pentaerythritol polyvalent acrylate or the like is 36%. (Example B) (Synthesis Example 2) 41 322127 201105694 A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Synthesis Example 2 was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjustment device ( Hydroxy valence: 92 mg KOH / g, hydroxyl equivalent: 609.9 g / Eq) 439.41 g (0.72 mol), 4-nonoxyphenol as a polymerization inhibitor 0. 25 g, dilauric acid as an amine esterification reaction catalyst Butyltin 0. 25g and stirred until homogeneous, so that the internal temperature is 50 °C. 1%。 The N0% content of the above-mentioned NC0 content was 0.1%, and the above-mentioned NC0 content was 0.1%. The amine ester acrylate of the present invention is obtained as the end point of the reaction at the following point. The average molecular weight (Mw = 5500, Mn = 1800) and the viscosity llPa · s (6 (TC). Further, the obtained amine ester acrylate system, the content of the amine ester acrylate is 74% (relative to the total amount) The ratio of the acrylate-free acrylate was 26%. (Example C) (Synthesis Example 3) In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjusting device, a raw material synthesis example 3 was added. a mixture of DPETriA, DPETtetraA' DPETpentaA, DPEThexaA and TPETA obtained in the middle (hydroxyl price: 120 mg KOH/g, hydroxyl equivalent: 466.7 g/Eq) 423.78 g (0.91 mol), 4-anthracene as a polymerization inhibitor The phenol is 0. 25g, the dibutyltin dilaurate as the amine esterification reaction catalyst is 0.25g and stirred until it becomes uniform 'the internal temperature is 50 ° C. Then, the internal temperature does not exceed 80 ° C 6% 曱 二 di diisocyanate 76. 22g (0. 45 mol), 42 322127 201105694 after the addition at 80. (: the next reaction for 6 hours, the above-mentioned NC0 content becomes 0.1% or less as the reaction end point, The amine ester acrylate of the present invention is obtained. The average molecular weight of the system (Mw = 780) 0, Mn = 1700), viscosity 16 Pa. s (60 〇 C). Further, the obtained amine ester acrylate type, amine ester acrylate content is 73% (ratio to total amount), without amine ester The content of the acrylate was 27%. (Example D) (Synthesis Example 4) DPETtetraA, DPETpentaA obtained in Synthesis Example 2 was added to a reactor equipped with a reflux condenser, a stirrer, and a thermometer 'temperature adjusting device' , a mixture of DPEThexaA and TPETA (hydroxyl: 92 mg KOH / g, hydroxyl equivalent: 609. 9g / Eq) 340. 10g (〇. 56mol), glycerol 4. 08g (0. 04mol), 2-butanone 100· 00g As a polymerization inhibitor, 4-milk milk. Basically 0. 20g, dibutyltin dilaurate 0. 20g as an amine oxime reaction catalyst and disturbed to become uniform 'the internal temperature is 5 〇. Then, the internal temperature was not more than 8 〇. The hexamethylene diisocyanate 55·83 g (0.33 mol) was added dropwise, and after the addition, the reaction was carried out at 80 ° C for 6 hours to obtain the above-mentioned NC0 content. 〇. 1% or less is used as the reaction end point. Heat to 60 C 'under reduced pressure to remove the solvent (2-butanone) to obtain the hair The amine acrylate ester This line average molecular weight (Mw = 10300, Mn = 18〇〇), viscosity igpa. S (6 (TC). Further, the content of the obtained amine ester acrylate type 'amino ester acrylate' is 74% (ratio to the total amount), and the amount of the unesterified acrylate having 43 322127 201105694 is 26%. . (Example E) (Synthesis Example 5) A mixture of DpETtetraA, DPETpentaA, DPEThexaA, and TPETA obtained by adding Raw Material Synthesis Example 2 to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjusting device (base price) : 92 mg KOH / g, hydroxyl equivalent: 609. 9g / Eq) 308. 78g (〇. 51mol), a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (parts by weight: 70/30, hydroxyl equivalent: 421. 9g/Eq) 29. 06g (0. 07mol), glycerol 4·23g (0. 05mol), 2-butanone 1〇〇·〇〇g, 4-methoxyphenol as a polymerization inhibitor 0. 20g, 20 g of dibutyltin dilaurate as an amine esterification reaction catalyst was stirred until homogeneous, and the internal temperature was 5 Torr. Hey. Then, so that the internal temperature does not exceed 8 〇.滴 方式 57 六 六 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 57 . The mixture was heated to 60 ° C, and the solvent (2-butanone) was distilled off under reduced pressure to give the amine acrylate of the present invention. The average molecular weight (MW ^ IUOO , Mn = 1, 7 〇〇) and the viscosity of 17 Pa · s (60 〇 C). Further, the content of the obtained amine ester acrylate-based amine ester acrylate was 74% (ratio to the total amount), and the content of the acrylate which was not esterified with the amine was 26%. (Example F) (Synthesis Example 6) A mixture of DPETtetraA, 322127 201105694 DPETpentaA, DPEThexaA and TPETA obtained in the raw material synthesis example 2 was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjusting device. Base price: 92 mg KOH / g, hydroxyl equivalent: 609. 9g / Eq) 325. 95g (0. 53mol), 2-ethyl methacrylate 8.44g (0. 07mol), glycerol 4.46 transport (0.05111 〇 1) 2克。 2-butanone 100. 00g, as a polymerization inhibitor 4-methoxyphenol 0. 20g, as an amine esterification reaction catalyst dibutyltin dilaurate 0. 20g and stirred until uniform, so that the internal temperature is 50 ° C. The first N0 content is 0.11. The time point below % is used as the reaction end point. Heating to 6 (TC, the solvent (2-butanone) was distilled off under reduced pressure to give the amine ester acrylate of the present invention. The average molecular weight of this system (Mw = 9, 500, Mn = 1,800), viscosity 17 Pa · s Further, the obtained amine ester acrylate type, the content of the amine ester acrylate was 74% (ratio to the total amount), and the content of the acrylate having no amine esterification was 26%. Example G) (Synthesis Example 7) A mixture of DPETtetraA, DPETpentaA, DPEThexaA, and TPETA obtained by adding Raw Material Synthesis Example 2 to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjusting device (hydroxyl price: 92 mg) KOH/g, hydroxyl equivalent: 609.9 g/Eq) 320.42 g (0.53 mol), acrylate 2-glycol g. 8.94 g (0.08 mol), glycerol 5.91 g (0. 〇6 mol), 2-butyl Ketone 100. 00g, 4-methoxyphenol oxime as a polymerization inhibitor. 20g, dibutyltin dilaurate as an amine esterification reaction catalyst. 2〇g and stirred until it becomes a hook, the internal temperature is 50 °C. Then, the internal temperature is not more than 45 322127 201105694 over 80 ° C into the six sulfhydryl diisocyanate 64.73g (0.38 mol After the addition, the reaction is carried out at 80 ° C for 6 hours, and the above-mentioned NC0 content is 0.1% or less as the reaction end point. The mixture is heated to 60 ° C, and the solvent (2-butanone) is distilled off under reduced pressure to obtain the present. The amine ester acrylate of the invention has an average molecular weight (Mw = 19, 700, Μη = 1,800) and a viscosity of 27 Pa · s (60 ° C). Further, the obtained amine ester acrylate type, amine ester acrylate content 75% (ratio to the total amount), the content of the unesterified acrylate is 25%. (Example H) (Synthesis Example 8) With a reflux condenser, a stirrer, a thermometer, and a temperature adjusting device In the reactor, a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Synthesis Example 2 (base price: 92 mg KOH/g, hydroxyl equivalent: 609.9 g/Eq) 330.55 g (0.54 mol), 2- butyl ketone 100. 00g, 4-methoxy phenol as a polymerization inhibitor 0. 20g, dibutyltin dilaurate as an amine esterification reaction catalyst 0. 20g and stirred until uniform, the internal temperature is 50 ° C. Then, in order to make the internal temperature not exceed 80 ° C into the hexamethylene diisocyanate 17. 36g (0. 10mol), TLA-100 (hexamethylene diisocyanate 3) 52. 09g (0. 10 moles), after the addition at 80 ° C for 6 hours, with the aforementioned NC0 content The time point of 0.1% or less was taken as the reaction end point. The mixture was heated to 60 ° C, and the solvent (2-butanone) was distilled off under reduced pressure to give the amine ester of the present invention. This series has an average molecular weight (Mw = 16, 300, Mn = 2,000) and a viscosity of 24 Pa s (60 〇 C). 46 322127 201105694 Further, the obtained amine ester acrylate type, the amine ester acrylate content was 74% (ratio to the total amount), and the content of the unesterified acrylate was 26%. (Example 1) (Synthesis Example 9) A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in the synthesis example 2 of the raw material was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjusting device (hydroxyl price: 92 KOH / g, hydroxyl equivalent: 609. 9g / Eci) 337. 88g (〇. 55mol), 2-butanone 100. 00g, as a polymerization inhibitor 4-methoxy phenol 〇. 2〇g, as The amine esterification reaction catalyst was dibutyltin dilaurate. 2 〇g and stirred until homogeneous, and the internal temperature was 50 °C. Then, the hexamethylene diisocyanate was added in an amount of 26.62 g (〇. 16 mol), TLA-100 (hexamethylene diisocyanate 3), 35. 50 g ( 0. 07摩尔), after the addition, the reaction was carried out at 80 ° C for 6 hours, and the above-mentioned NC0 content was 0.1% or less as the reaction end point. The amine ester acrylate of the present invention is obtained by heating to 6 ° C and desolvating the solvent (2-butanone) under reduced pressure. This system has an average molecular weight (Mw = 8,500, Mn = 1,800) and a viscosity of 12 Pa · s (60 ° C). Further, the obtained amine ester acrylate type, the content of the amine ester acrylate was 74% (ratio to the total amount), and the content of the acrylate which was not esterified with the amine was 26%. (Example J) (Synthesis Example 1) A mixture of DpETtetraA, 47 322127 201105694 DPETpentaA, DPEThexaA and TPETA obtained in the raw material synthesis example 1 was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjustment device. (hydroxyl: 80 mg K〇H/g, hydroxyl equivalent: 701.4 g/Eq) 331. 80 g (0.54 mol), 2-butanone 100. 00 g, 4-methoxyphenol oxime as a polymerization inhibitor. 20 g 20 g of dibutyltin dilaurate as an amine esterification reaction catalyst was stirred until uniform, and the internal temperature was 50 °C. Then, the amount of the hexamethylene diisocyanate was 7. 58 g (0.05 mol), and the TLA-100 (hexamethylene diisocyanate 3 mass) 60. 62 g (in a manner such that the internal temperature did not exceed 80 ° C). 0. 12 mol) After the addition, the reaction was carried out at 80 ° C for 6 hours, and the time point at which the above-mentioned NC0 content became 0.1% or less was used as the reaction end point. Heat to 6 〇. (: The solvent (2-butanone) was distilled off under reduced pressure to obtain an amine ester acrylate of the present invention. The average molecular weight of the system (Mw = 11,700, Μη = 1,800), viscosity 23 Pa. s (60 〇 C) Further, the obtained amine ester acrylate type, the content of the amine ester acrylate was 66% (ratio to the total amount), and the content of the acrylate having no amine esterification was 34 ° / 〇. (Example K (Synthesis Example 11) A mixture of DPHtetraA, DPETpentaA, DPEThexaA, and TPETA obtained in Synthesis Example 2 was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjustment device (hydroxyl price: 120 mg KOH/g) , hydroxyl equivalent: 467. 6g / Eq) 305. 74g (0. 50mol), 2-butanone 100. 00g, as a polymerization inhibitor 4-methoxyphenol oxime. 20g, as an amine esterification reaction catalyst 2 曱 二 二 异 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 47 06莫), 48 322127 201105694 TLA-100C hexamethylene diisocyanate 3 body) 83. 79g (0. 17m) After the addition, the reaction was carried out at 80 ° C for 6 hours, and the time point of the above-mentioned NC0 content was 0.1% or less as the reaction end point. The mixture was heated to 60 ° C, and the solvent (2-butanone) was distilled off under reduced pressure to give the amine ester acrylate of the present invention. This system has an average molecular weight (Mw = 27,700, Mn = 2,000) and a viscosity of 32 Pa · s (60 ° C). > Further, the obtained amine ester acrylate type, the amine ester acrylate content was 74% (ratio to the total amount), and the content of the unesterified acrylate was 26%. (Comparative Synthesis Example 1) A mixture of DPETtetraA, DPETpentaA, DPEThexaA, and TPETA obtained in Comparative Raw Material Synthesis Example 1 was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjustment device (base price: 45 mg) KOH/g, hydroxyl equivalent: 1246.9 g/Eq) 473. 39 g (0.38 mol), 4-nonoxyphenol as a polymerization inhibitor, 0. 25 g, dibutyltin dilaurate as an amine esterification reaction catalyst 25 g and stirred until homogeneous, so that the internal temperature was 50 °C. Then, in a manner such that the internal temperature does not exceed 80 ° C, 26.61 g (0.16 mol) is added, and after the addition, the reaction is carried out at 80 ° C for 6 hours, and the above-mentioned NC0 content becomes 0. The time point below 1% is used as the reaction end point to obtain an amine ester acrylate. The average molecular weight of this system is =^= 2,200,1^=1,200), viscosity 2?&·s(60°C) °, and the obtained amine ester acrylate type, the content of amine ester acrylate is 48%. (relative to the total ratio), the amount of 49 322127 201105694 without the esterification of the acrylate is 52%. (Comparative Synthesis Example 2) A mixture of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA, and TPETA obtained in Comparative Raw Material Synthesis Example 2 was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjustment device (hydroxyl price: 140 mg KOH / g, hydroxyl equivalent: 400. 8g / Eq) 413 · 28g (l · 〇 3mol), 4-nonoxyphenol as a polymerization inhibitor 0. 25g, dilauric acid as an amine esterification reaction catalyst Dibutyltin 〇. 25g and stirred until homogeneous, so that the internal temperature is 50 °C. Then, 86.72g (0. 52 moles) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 ° C. After the addition, the reaction was carried out for 2 hours to cause gelation, and the desired amine ester acrylic acid could not be obtained. ester. (Comparative Synthesis Example 3) A mixture of DPETtetraA, DPETpentaA, DPEThexaA, and TPETA obtained in Synthesis Example 2 was added to a reactor equipped with a reflux condenser, a scrambler, a thermometer, and a temperature adjustment device (hydroxyl price j2 mg KOH/ g, base equivalent: 609. 9g / Eq) 316 · 79g (0. 52mol), 4-methoxy benzene as a polymerization inhibitor. 25g, dibutyl tin dilaurate as a catalyst for amine acetation reaction G.25g was disturbed until it became uniform, so that the internal temperature was 50 °C. Then, the internal temperature was not more than 8 (rc was dropped into TLA_100 (/, methylene-iso-same vinegar 3) 83 21 g (〇16 mol), and then reacted at 80 Torr for 4 hours. Gelation occurred, and the desired amine ester acrylate could not be obtained. (Comparative Synthesis Example 4) 322127 50 201105694 DPETtriA obtained in Synthesis Example 3 was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature adjustment device. , DPETtetraA, DPETpentaA, DPEThexaA and TPETA mixture (hydroxyl price: 120mg KOH / g, hydroxyl equivalent: 466.7g / Eq) 297. 93g (0 · 49mol), as a polymerization inhibitor 4-nonoxyphenol oxime. 25 g, dibutyltin dilaurate, which is an amine acetation reaction catalyst, 25 g and stirred until homogeneous, so that the internal temperature is 50 ° C. Then, the internal temperature does not exceed 80. (: The method of dropping into TLA- 100C hexamethylene diisocyanate 3) 102·07 g (0.20 mol) After the addition, the reaction was carried out at 8 ° C for 2 hours to cause gelation, and the desired amine ester acrylate could not be obtained. 1 to 4 and Comparative Examples 1 to 2) are formulated in the composition shown in Table 1. The components are mixed until homogeneous, and the resin composition of the present invention and the resin composition of the comparative example are prepared. Each of the obtained resin compositions is applied to a PET film by a bar coater (film thickness 125). //in), about 8 〇 to l〇〇t: dry. Each of the obtained coating films is irradiated with ultraviolet rays by a UV irradiator (JAPAN STORAGE BATTERY CO'LTD.: CS 30L-:ll) to make a coating film. Hardening to obtain a PET film (hard coat film) having a hard coat layer having a film thickness of about 5 #m. Further, the curing conditions are as follows. Hardening conditions: high pressure mercury lamp: 120 W/cm, lamp height: 10 cm, transport Belt speed: 10 m/min (irradiation energy: about 300 mW/cm2, about 200 mJ/cm2) 〇 and the unit of the numerical value in Table 1 means "parts by mass". 51 322127 201105694 [Table 1] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Compound 50 of Synthesis Example 1 Compound 50 of Synthesis Example 2 40 Compound 50 of Synthesis Example 3 Comparative Compound 50 of Synthesis Example 1 DPHA *1 10 50 MEK *2 50 50 50 50 50 50 Irg. 184*3 5 5 5 5 5 5 (8) *1.DPHA: dipentaerythritol pentaacrylate/hexaacrylate mixture *2.MEK ··mercaptoethyl ketone*3. Irg. 184 : Ciba Specialty Chemicals The 1-, 4-cyclohexyl phenyl ketone was evaluated for the hard coat films obtained in Examples 1 to 4 and Comparative Examples 1 to 2, and the results are shown in Table 2. (Pencil Hardness) The pencil hardness of the obtained hard coat film was measured in accordance with JIS K 5600-5-4 using a pencil scratch tester. Specifically, on the polyester film having the measured hardened film, the pencil is applied with a load of 75 Og from above at an angle of 45 degrees to about 5 mm, and the pencil is not scratched four times or more in five times. Hardness is expressed. (Adhesion) The surface of the hard-coated film obtained after the light resistance test was scratched by a cutter 52 322127 201105694 and the ground (30 sides 1), and the adhesive tape was attached from above, at an angle of 90 degrees. Stripped. 〇: No peeling x: Peeling (scratch resistance) A load of 200 g/cm 2 was applied to the steel wool #0000, and the scratch was observed visually 1 G times on the surface of the obtained hard film. 〇: No scratches x: Produced to injury (curl) Drying furnace:: Hard: The film is cut into 5,5αη, placed on the dry side of 8 "C". The measured value (unit: brain) was measured on the water platform. At this time, the curl of the explosive material itself is 〇_.呀 (Appearance) The state of whitening, haze, etc. The surface crack is judged by the naked eye. Evaluation: Good X. Significant cracks occur [Table 2]

322127 53 201105694 攸, 2 results clearly show that the thin film of the hardened film obtained by making the resin composition of the present invention has hardness, adhesion, and crack-resistant good cracking, compared with the comparative example , curly small. (Examples 5 to 7 and Comparative Example 3) ^ q The composition of each of the components in Table 3 was adjusted to be uniform, and the resin composition of the present invention and the abundance of the comparative example were prepared. Each of the obtained resin compositions was coated on a non-stick board with a bar coating H. Each of the coating films of = to J was irradiated with ultraviolet rays by an ultraviolet ray irradiator (Japan Battery Co., Ltd.) to harden the coating film. The thickness of each of the obtained cured films was about 200 yin. The cured film was peeled off from the non-transferred steel sheet to obtain a cured film for testing. Further, the curing conditions are as follows. Hardening conditions: high pressure mercury lamp: 80 W/cm, lamp height: 1 〇 cm, belt speed: 5 m/min (irradiation energy: about 9 〇〇 mW/cm2, about 6 〇〇 m" cm2). Further, the unit of the numerical value in Table 3 indicates "parts by mass". 54 322127 201105694 [Table 3] Example 5 Example 6 Example 7 Comparative Example 3 Compound of Synthesis Example 1 Compound of Synthesis Example 2 Compound 80 of Synthesis Example 3 Comparative Compound 80 of Synthesis Example 1 HDDA *4 20 20 20 20 Irg. 184 3 3 3 3 (Note) *4. HDDA ··1,6-hexanediol diacrylate (tensile test) According to JIS K 7162, it was obtained from Examples 5 to 7 and Comparative Example 3. The film was prepared into a dumbbell-shaped test piece, and the following data was measured using a tensile tester. The evaluation results are shown in Table 4. 1: Young's modulus (丫011叩'3 1110(1111113) (elasticity) 2: breaking point stress 3: breaking point elongation [Table 4] Young's modulus (MPa) Breaking point stress (MPa) Breaking point Elongation (%) Example 5 1050 13.8 1.5 Example 6 1070 15.2 1.8 Example 7 1060 17.9 2.1 Comparative Example 3 1020 9.7 1.0 55 322127 201105694 From the results of Table 4, it was found that the resin composition of the present invention was cured. The hardened film system has a large crack stress point and a large break point, and is softer and stronger than the comparative example. (Examples 8 to 15) The components were blended in the composition shown in Table 5 below, and mixed until homogeneous. Further, the "MEK" and "Irg. 184" in the table have the same meanings as in Table 1. The obtained resin compositions were obtained in the same manner as in the above Examples 1 to 4. A PET film (hard coat film) having a hard coat layer having a film thickness of about 5/zm. The obtained hard coat film was evaluated in the same manner as in Examples 1 to 4, and the results are shown in Table 6 below. Table 5] Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Compound of Synthesis Example 4 Compound 50 of Synthesis Example 5 Compound of Synthesis Example 6 Compound of Synthesis Example 7 Compound of Synthesis Example 8 Compound of Synthesis Example 9 Synthesis Example 10 Compound 50 Compound 50 of Synthesis Example 11 MEK *2 50 50 50 50 50 50 50 50 Irg. 184*3 5 5 5 5 5 5 5 5 56 322127 201105694 [Table 6] Pencil hardness Adhesive scratch-resistant curl appearance Example 8 3H 〇〇16 〇Example 9 3H 〇〇17 〇Example 10 3H 〇〇17 〇Example 11 3H 〇〇16 〇Example 12 3H 〇〇16 〇Example 13 3H 〇〇18 〇Example 14 3H 〇〇16 〇 Example 15 3H 〇〇15 〇 From the results of Table 6, it is understood that the film having the hardened film obtained by curing the resin composition of the present invention has hardness, adhesion, and scratch resistance. It has good properties and no cracking occurs. The hardness and adhesion of the hardened film obtained by hardening the resin composition of the present invention It has good scratch resistance and no cracking, and maintains the characteristics required as a hard coat layer, and has the characteristics of small curl, soft and strong characteristics. (Industrial Applicability) The hard coat film obtained by curing the resin composition of the present invention is excellent in hardness, adhesion, and scratch resistance, and does not cause curling or cracking. Therefore, the resin composition of the present invention is suitable as a material for a hard coat layer of a plastic film or a small frame, a color filter, a black matrix, and a spacer. [Simple diagram description] None [Main component symbol description] None 57 322127

Claims (1)

201105694 VII. Patent Application Range: 1. An amine ester (meth) acrylate compound (A) which is (丨) any one of the following (i), (ii) or (iii) and (11) The polyisocyanate compound (b) containing a diisocyanate compound is obtained by reacting: (i) comprising dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate And a mixture of dipentaerythritol hexa(meth) acrylate and y 2 groups and a base [ gt; 80 to 120 mg KOH / g of dipentaerythritol poly (meth) acrylate mixture (a) (below Known as the mixture (a)); (ii) both the mixture (a) and glycerin; or un) the mixture (a), glycerin and 02 to C5 aliphatic poly (2 to 4) alcohol (methyl) ) 3 of acrylates. 2. The amine ester (meth) acrylate compound (A) as described in the scope of claim 2, wherein (I; ^(i) the mixture (a). 3. As claimed in claim 1 Aminoester (meth)acrylated 5 (A) ' wherein (II) the polyisocyanate compound (匕) is a diisocyanate compound alone or a diisocyanate compound and a triisocyanate compound are combined with a 'diisocyanate compound and three The ratio of the isocyanate compound is based on the diisocyanate compound 丨mol, and the triisocyanate compound is a ratio of 〇 to 1 〇mol. 4. The amine ester (mercapto) acrylate compound (A) as described in the scope of claim ), which is represented by the following general formula (1): 322127 58 201105694 (wherein X is an isocyanate residue, η is an integer from 〇 to loo, and Υ is an organic group represented by the following formula (2), wherein a, b and c are l$aS4, 0Sb$3 and An integer of 0$〇^3, and 3 +乜+ c = 4, A is an organic group represented by the above formula (2), wherein X is an isocyanate residue 'c is 0, a and b are integers of 1Sa$5, 〇Sb'4, and a + b = 5, B is an organic group represented by the above formula (2), wherein X is an isocyanate residue, C is 0, 9 and b are as follows: (i) when Β is present at the end, in the formula S4 The integer ' and a + b = 5, (li) B exists outside the end, where 8 and 13 are integers, and a + b = 4). 5. The amine ester (meth) acrylate 5Q ^ 322127 201105694, the method for producing the compound (A), which is based on the active hydrogen group in the mixture (a) , the isocyanate group equivalent weight of the polyisocyanate compound (b) is from 0.1 to 50 equivalents, such that (I). (丨) the mixture (a) and (II) polyisocyanate compound (b;) reaction. 6. The amine ester (meth) acrylate compound (A) as described in claim 1 wherein '(I) is (ii) the mixture (a) and glycerin.至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至The ratio of the isocyanate group equivalent in the equivalent (Η) polyisocyanate compound (b) is from 1 to 5 equivalents, and the mixture (a) and glycerin in the first claim of the patent application range, and the first item of the patent application range The (II) polyisocyanate compound is reacted. 8. A resin composition comprising the bismuth (meth) acrylate compound (A), (mercapto) acrylate (b) and photopolymerization described in claim 1 Starting agent (C). 9. The resin composition according to item 8 of the patent application, which is used for a hard coat layer. 10. The amine ester (mercapto) acrylate compound (A) according to claim 1, wherein (I) is (iu) the mixture (a), glycerin and 匸2 to C5 aliphatic plural ( 2 to 4) 3 of the (meth) acrylates. 11. A method for producing an amine ester (meth) acrylate compound (A) according to claim 1, wherein the active hydrogen of glycerol is 1 equivalent to the active hydrogen group in the mixture (a) The (meth)acrylic acid 322127 60 201105694 ester having a base equivalent of 〇.〇1 to 1〇 equivalent and a C2 to C5 aliphatic polybasic (2 to 4) alcohol has an active hydrogen group equivalent of 0.01 to 10 equivalents, polyisocyanate The isocyanate group equivalent of the compound (b) is 〇.; [to a ratio of 50 equivalents, (iii) (iii) the mixture (a), glycerin and C2 to C5 aliphatic plural (2) Up to 4) 3 of the (meth) acrylate of the alcohol, and reacted with the (11) polyisocyanate compound (b) described in the first aspect of the patent application. 12. The amine ester (mercapto) acrylate compound (A) according to claim 1, wherein the mixture (a) in (1) is based on the total amount of the mixture (3). In the area ratio (%) of high performance liquid chromatography (HPLC), 35 to 6 % of dipentaerythritol penta (meth) acrylate is contained, and dipentaerythritol tetra (meth) acrylate and dipentaerythritol are further added thereto. The total of the three after the hexa(methyl) acrylate is g 〇 to 1 〇〇 %, and the remainder 0 to 10% is a multi-quantity of dipentaerythritol tri(meth) acrylate and tripentaerythritol (曱Base) acrylate. 13. The amine ester (meth) acrylate compound (A) as described in claim 12 or 12 wherein the polyisocyanate compound (b) is a diisocyanate compound alone. 14. The amine acetoacetate (A) as described in claim 1 or 12 wherein the polyisocyanate compound (b) is a combination of a diisocyanate compound and a triisocyanate compound. . 15. The amine acetonate (meth) acrylate vinegar & (A) according to claim 13, wherein the diisocyanate compound is hexamethylene diisocyanate. 16. The amine vinegar (meth)acrylic acid g 322127 61 201105694 compound (A) according to claim 1, wherein the mixture (di) is dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate And a mixture of three of dipentaerythritol hexaacrylate, or a mixture of dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, and the polyisocyanate compound is hexamethylene The diisocyanate is either alone or both of hexamethylene diisocyanate and hexamethylene diisocyanate. A resin composition comprising the amine ester (mercapto) acrylate compound (A) and the photopolymerization initiator (c) according to claim 1 of the patent application. A cured film of a resin composition comprising the amine ester (meth) acrylate compound (A) and the photopolymerization initiator (C) according to claim 1 of the patent application. 19. The amine ester (mercapto) acrylate compound (A) according to claim 1, wherein the viscosity (60. 〇 is 5 to 40 Pa. s. 322127 62 201105694 IV. Designated representative figure: the case No picture (1) The representative picture of the case is: () picture. (2) Simple description of the symbol of the representative figure·· 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: Representative chemical formula 3 322127