JP2013072009A - Hot-melt adhesive film, and hot-melt adhesive film laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hot-melt adhesive film laminate capable of preventing a hot-melt adhesive composition from being deposited onto a punch and a die in fine and high-speed perforation punching work.SOLUTION: The hot-melt adhesive composition includes a saturated polyester resin, a storage elastic modulus (G') is 1×10Pa or more to 1×10Pa in 10-40°C of temperature range, a loss elastic modulus (G") is 1×10-1×10Pa in 100-150°C of temperature range, and a thickness is 5-50 μm, in the hot-melt adhesive film laminate.

Description

The present invention relates to a hot melt adhesive film and a hot melt adhesive film laminate suitable for precision punching.

  The hot-melt adhesive film can be obtained by a punching machine using a press with a shear, such as a die composed of a punch, a stripper plate and a die, after being thermally bonded to the single body or a sheet or film-shaped adherend. The size and shape may be stamped. In recent years, the demand for precise punching size has increased, and the punch-die clearance is often set to 0.03 mm or less. When these precision punching processes are mass-produced continuously, in consideration of productivity, a pair of punches and / or dies may be punched at a high speed of 50 to 1000 times per minute. At this time, the hot-melt adhesive composition adheres to the die punch and / or die cutting edge and the cut surface of the punched product, or adheres to the side surface of the punch, and the punched debris composed of the deposited adhesive component is formed. , Scraped off by a stripper plate, removed from the punch and adhered as a foreign matter to the product, which sometimes resulted in a defective product. In order to avoid these problems, it is necessary to stop the device and periodically clean the punch and / or die every time a certain number of precision punching processes are performed. The precision punching process itself can be performed at high speed. Regardless, there is a problem that the processing speed of the process is not so improved.

  As a technique for solving such a problem, for example, in the case of punching, a stripper plate provided with a wetting member that wets the outer peripheral surface of the punch with a sponge-like member or the like in which a liquid such as ethanol or alcohol is impregnated is used. Is known (Patent Document 1).

  However, in these technologies, it is important that the part of the punch that comes into contact with the workpiece is always kept wet with the wetting liquid, and the punching machine equipment is periodically stopped. In other words, it was necessary to carry out replenishment of the wetting liquid, which was inadequate in terms of improving the processing speed.

JP 2009-214251 A

  In view of the background of the prior art, the present invention is to provide a hot melt adhesive film laminate that is suitable for precision punching molding and hardly causes the hot melt adhesive composition to adhere to a punch and a die.

The present invention employs the following means in order to solve such problems. That is,
(1) Storage modulus (G ′) in a temperature range of 10 ° C. to 40 ° C. containing a saturated polyester resin has a loss in a temperature range of 1 × 10 ⁶ to 1 × 10 ¹⁰ Pa and 100 ° C. to 150 ° C. A hot melt adhesive film having a thickness of 5 to 50 μm, comprising a hot melt adhesive composition having an elastic modulus (G ″) of 1 × 10 ¹ to 1 × 10 ⁴ Pa.
(2) A hot melt adhesive film laminate in which a carrier film made of a plastic film having a Young's modulus of 2 to 15 GPa or more is laminated on one side or both sides of the hot melt adhesive film according to (1).
(3) The hot melt adhesive film laminate according to (2), wherein the ratio of the thickness of the hot melt adhesive film to the thickness of the carrier film is 0.2 to 1.0.

  ADVANTAGE OF THE INVENTION According to this invention, the hot-melt-adhesive film and hot-melt-adhesive film laminated body which are hard to produce adhesion of the hot-melt-adhesive composition to a punch and die | dye suitable for precision punching can be provided.

It is a graph of the storage elastic modulus (G ') and the loss elastic modulus (G ") of the hot melt adhesive composition A. It is a graph of the storage elastic modulus (G ') and the loss elastic modulus (G ") of the hot melt adhesive composition B. It is a graph of the storage elastic modulus (G ') and the loss elastic modulus (G ") of the hot melt adhesive composition C. It is a graph of the storage elastic modulus (G ') and loss elastic modulus (G ") of the hot melt adhesive composition D. It is a graph of the storage elastic modulus (G ') and loss elastic modulus (G ") of the hot melt adhesive composition E.

  The present invention relates to the above-mentioned problem, that is, a hot melt adhesive film and a hot melt adhesive film laminate that are suitable for precision punching, specifically, the hot melt adhesive composition does not adhere to the punch and die by precision punching. The present inventors have intensively studied and found that this problem can be solved at once by arranging a hot melt adhesive film made of a saturated polyester resin having a specific storage elastic modulus (G ′) and loss elastic modulus (G ″). Is.

  The hot melt adhesive composition used for the hot melt adhesive film of the present invention contains a saturated polyester resin. Hot melt adhesive compositions include those containing saturated polyester resins, (meth) acrylic resins, polyolefin resins, ethylene-vinyl acetate copolymer resins, polyamide resins, chloroprene resins, etc. Generally, the type and melting point are appropriately selected and used depending on the use temperature of the bonded material, but in the present invention, among these, those containing a saturated polyester resin are those having adhesive strength with a substrate and heat resistance. It is preferably used from the viewpoint of sex.

  The thickness of the hot melt adhesive film of the present invention is 5 to 50 μm. More preferably, it is 5-30 micrometers. When the thickness is less than 5 μm, the area where the punch or die blade side surface and the cut surface of the hot melt adhesive film are in contact with each other when performing precision punching is small, so the hot melt adhesive composition is applied to the punch or die. Although it becomes difficult to adhere, pinholes may be generated due to scratches during the production of the hot-melt adhesive film itself, or the desired adhesive strength may not be obtained due to the thin thickness. As a result, variations in adhesive strength may occur. Also, if the thickness of the hot melt adhesive film is greater than 50 μm, when heat bonding with the non-adherent body, the heat conduction deteriorates, resulting in variations in adhesive strength, or the hot melt adhesive composition is melted by heat. In some cases, an adhesive flow is generated, and other than the desired bonded portion is soiled.

The hot melt adhesive composition used in the present invention is a saturated polyester resin having a storage elastic modulus (G ′) in a temperature range of 10 ° C. to 40 ° C. of 1 × 10 ⁶ to 1 × 10 ¹⁰ Pa. The storage elastic modulus (G ′) in the temperature range of 10 ° C. to 40 ° C. is preferably 1 × 10 ⁷ to 1 × 10 ⁹ Pa. The storage elastic modulus (G ′) in the temperature range of 10 ° C. to 40 ° C. is 1 × 10 ⁶ to 1 × 10 ¹⁰ Pa. The storage elastic modulus (G ') Represents that it is in the range of 1 × 10 ⁶ to 1 × 10 ¹⁰ Pa. When there is a temperature at which the storage elastic modulus (G ′) is less than 1 × 10 ⁶ Pa in a temperature range of 10 ° C. to 40 ° C., the hot melt adhesive composition is applied to the punch and / or die in continuous punching molding. However, if the storage elastic modulus (G ′) is 1 × 10 ⁶ Pa or more at any temperature in the temperature range from 10 ° C. to 40 ° C., the hot melt adhesive composition adheres to the punch and die. This makes it possible to perform punching continuously. This is because by performing a precision punching process, frictional heat or the like is generated between the punch and the punching material and the die, and the punch and / or the die itself accumulates heat, resulting in a temperature of 10 ° C to 40 ° C. When the punch and / or die at that temperature come into contact with the hot melt adhesive composition at the cut surface, the hot melt adhesive composition softens and the hot melt adhesive composition adheres to the side of the punch. However, when the storage elastic modulus (G ′) in the temperature range of 10 ° C. to 40 ° C. is 1 × 10 ⁶ Pa or more, the hot melt component does not adhere to the side surface of the punch. When there is a temperature at which the storage elastic modulus (G ′) is larger than 1 × 10 ¹⁰ Pa in a temperature range of 10 ° C. to 40 ° C., a hot melt adhesive film having a high adhesion temperature when used as a hot melt adhesive film is obtained. This is because the productivity of the applied product is deteriorated, and the base film and / or the adherend are damaged by heat, such as deterioration and deformation.

  The storage elastic modulus (G ′) referred to here means viscoelasticity with a measurement frequency of 1 Hz due to shear deformation. The dynamic viscoelasticity includes tension, compression deformation and shear deformation. The viscoelasticity of tension and compression deformation uses symbols such as E, E ′ and E ″, and the viscoelasticity of shear deformation is G and G. It is common to use symbols such as', G ". The storage elastic modulus (G ′) and the loss elastic modulus (G ″) in the present invention use viscoelasticity at a measurement frequency of 1 Hz in shear deformation, but between E and G, the following formulas (1) and (2) There is a relationship, and it can be read as storage elastic modulus (E ′) and loss elastic modulus (E ″) obtained by measuring viscoelasticity of tension and compression deformation.

E ′ = 2G ′ (1 + ν) (1)
E ″ = 2G ″ (1 + ν) (2)
ν: Poisson's ratio The hot melt adhesive composition used in the present invention has a loss elastic modulus (G ″) in a temperature range of 100 ° C. to 150 ° C. of 1 × 10 ¹ to 1 × 10 ⁴ Pa, preferably 1 × 10 ² to 1 × 10 ⁴ Pa, more preferably 1 × 10 ² to 1 × 10 ³ Pa. Loss elastic modulus (G ″) in a temperature range of 100 ° C. to 150 ° C. is 1 × 10 ¹ to 1 X10 ⁴ Pa represents that the loss elastic modulus (G ″) is in the range of 1 × 10 ¹ to 1 × 10 ⁴ Pa at any temperature from 100 ° C. to 150 ° C. When the loss elastic modulus (G ″) is lower than 1 × 10 ¹ Pa in the temperature range of 100 ° C. to 150 ° C., the hot melt adhesive composition is used when performing heat sealing with the adherend. Will flow and give seal heat Tackiness is lost in time, it may become peeled off from the adherend before itself the hot melt adhesive composition is cooled and solidified. If there is a temperature at which the loss elastic modulus (G ″) in the temperature range of 100 ° C. to 150 ° C. exceeds 1 × 10 ⁴ Pa, the fluidity during heating when used as a hot melt adhesive film is small, In some cases, the area to be bonded to an uneven adherend is reduced, and the adherend is not firmly bonded. Loss elastic modulus (G ″) in a temperature range of 100 ° C. to 150 ° C. is 1 × 10 ¹ to 1 ×. When it is 10 ⁴ Pa, when heat sealing is performed, it is possible to bond firmly without peeling off due to sealing heat or reducing the bonding area.

  The saturated polyester resin contained in the hot melt adhesive composition used in the present invention can be produced by reacting a dicarboxylic acid and a diol.

  The dicarboxylic acid used for the production of the saturated polyester resin contained in the hot melt adhesive composition used in the present invention is not particularly limited. For example, terephthalic acid, dimethyl terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalene Aromatic dicarboxylic acids such as dicarboxylic acid, succinic acid, glutaric acid, adipic acid, β-methyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, hexadecanedicarboxylic acid and the like, and 1,3 -Cycloaliphatic dicarboxylic acid, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and the like. These dicarboxylic acids may be used alone or in combination of two or more. In order to obtain the specific storage elastic modulus (G ′) in the present invention, among these, terephthalic acid, isophthalic acid, adipic acid, sebacic acid, etc. Group dicarboxylic acids are often used. Further, it is preferable to use a combination of terephthalic acid and isophthalic acid and an aliphatic dicarboxylic acid having 5 to 11 carbon atoms, particularly 5 to 10 carbon atoms, and terephthalic acid and 5 to 11 carbon atoms, particularly 5 to 5 carbon atoms. It is more preferable to use 10 aliphatic dicarboxylic acids in combination. In place of the dicarboxylic acid, acid anhydrides, esters, acid chlorides and the like can also be used. Moreover, some dicarboxylic acid components can be copolymerized with an unsaturated acid such as maleic acid, fumaric acid or dimer acid, and a trifunctional or higher polyfunctional acid such as trimellitic acid. The saturated polyester resin obtained by copolymerization of these monomers can be preferably used for imparting adhesiveness and at the same time obtaining a specific loss elastic modulus (G ″) in the present invention.

The diol used for the production of the saturated polyester resin contained in the hot melt adhesive composition used in the present invention is not particularly limited. For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1, 3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 3-methylpentanediol, 1,3-hexanediol, 1,6-hexanediol, 1,8- Octanediol, 1,9-nonanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol 1,4-cyclohexanediol, hydrogenated bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol, Trimethylolpropane, pentaerythrito Aliphatic polyhydric alcohols such as sulfur, 1,4-cyclohexanedimethanol, aliphatic diols having an alicyclic structure such as 1,3-cyclohexanedimethanol, ethylene oxide or propylene oxide adducts such as bisphenol S and bisphenol A, polyethylene Examples include diols such as polyalkylene glycols such as glycol, polypropylene glycol, and polytetramethylene glycol. These diols may be used alone or in combination of two or more. Of these, alkyl diols having 3 to 6 carbon atoms such as 1,4-butanediol and 1,6-hexanediol are often used. Moreover, as a diol, a C3-C5 alkyldiol is preferable and especially 1, 4- butanediol is more preferable. Further, some diol components can be copolymerized with a trihydric or higher polyhydric alcohol such as trimethylolpropane and pentaerythritol. The saturated polyester resin obtained by copolymerization of these monomers can be preferably used for imparting adhesiveness and at the same time obtaining a specific loss elastic modulus (G ″) in the present invention.
The saturated polyester resin contained in the hot melt adhesive composition used in the present invention has a dicarboxylic acid residue of 40 to 80 mol%, preferably 50, when the total amount of dicarboxylic acid residues is 100 mol%. When phthalic acid residues such as terephthalic acid residues are contained in 70 mol% and the total amount of diol residues is 100 mol%, it is 30 mol% or more (may be 100 mol%). A resin containing a butanediol residue such as 1,4-butanediol or 1,4-hexanediol or hexanediol is particularly preferable.

  The method for producing the saturated polyester contained in the hot melt adhesive composition used in the present invention is not particularly limited, and can be produced by a known polyester production method. For example, dicarboxylic acid and diol are used as raw materials, and after esterification or transesterification reaction at a temperature of 150 to 280 ° C. by a conventional method, a polycondensation catalyst is added and 200 to 300 ° C. under a reduced pressure of 5 hPa or less, preferably It can prepare by performing a polycondensation reaction at the temperature of 230-280 degreeC.

The saturated polyester resin contained in the hot melt adhesive composition used in the present invention has a mass average molecular weight (measured by gel permeation chromatography (GPC), polystyrene equivalent) of 8,000 to 100,000. Is preferred. When the mass average molecular weight is less than 8,000, the storage elastic modulus (G ′) in the temperature range from 10 ° C. to 40 ° C. is smaller than the specific range defined in the present invention, lacks cohesion, and adheres. In some cases, the strength, in particular, the adhesive strength at a high temperature is lowered, and the softening temperature is also reduced. Further, when the mass average molecular weight is larger than 100,000, the loss elastic modulus (G ″) in the temperature range of 100 ° C. to 150 ° C. is larger than the specific range of the present invention, or the melt viscosity at the time of coating. In order to reduce the viscosity of the hot melt adhesive composition, a high heat bonding temperature is required. In the process of laminating the base film, the production rate is remarkably reduced or the hot melt adhesive film is heated on the adherend. When bonding, it is necessary to increase the bonding temperature, and as a result, problems such as heat shrinkage of the base film and / or adherend, heat loss such as decomposition and melting may occur. A preferred saturated polyester resin in the present invention has a mass average molecular weight of 10,000 to 80,000. The mass average molecular weight is determined by the polymer obtained by the polycondensation reaction. And / or glycol added can also be prepared by a method of performing depolymerization reaction at a temperature of 220 to 280 ° C..
The hot melt adhesive composition used in the present invention may contain a polyethylene resin. As the polyethylene resin, for example, those obtained by copolymerizing various polyethylene resins and poly-α-olefins can be used. Examples of the polyethylene resin include low density polyethylene, linear low density polyethylene, and medium density polyethylene. These polyethylene resins may be used alone or in combination of two or more.
The content of the polyethylene resin is not particularly limited, but can be 5 to 30 parts by mass, particularly 10 to 25 parts by mass when the saturated polyester resin is 100 parts by mass. By containing 5 to 30 parts by mass of polyethylene resin, the processability and anti-blocking properties when forming into pellets and films can be further improved, and the cohesive strength of the hot melt adhesive composition can be increased. Can do.
The hot melt adhesive composition used in the present invention may contain an epoxy resin. The epoxy resin is not particularly limited. For example, bisphenol A type epoxy resin, novolac type epoxy resin, and the like can be used, but bisphenol A type epoxy resin and cresol novolac type epoxy having two or more glycidyl groups in the molecule. Resins are preferred. These epoxy resins may be used alone or in combination of two or more. For example, when the storage elastic modulus (G ′) in the temperature range of 10 ° C. to 40 ° C. is smaller than the specific range defined in the present invention, the epoxy resin is included so as to be adjusted to a specific range. be able to.
Although content of an epoxy resin is not specifically limited, When a saturated polyester resin is 100 mass parts, it can be 3-15 mass parts, especially 5-10 mass parts. By containing 3 to 15 parts by mass of an epoxy resin, a hot melt adhesive composition having sufficient initial adhesive strength, heat resistance, water resistance and the like can be obtained.
The hot melt adhesive composition used in the present invention may contain an organic alkoxysilane. The organic alkoxysilane is not particularly limited, and examples thereof include vinyltriethoxysilane, vinyltrimethoxysilane, vinyl-tri (β-methoxy) silane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropyl-tri (β -Methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxy Examples thereof include silane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane. Of these, an organoalkoxysilane having an epoxy group is particularly preferable.
Although content of organic alkoxysilane is not specifically limited, When a saturated polyester resin is 100 mass parts, it is preferable that it is 0.1-5 mass parts, especially 0.3-3 mass parts. By including 0.1 to 5 parts by mass of organoalkoxysilane, the initial adhesive strength, the adhesion strength to the substrate, and the like can be further improved.
The hot melt adhesive composition used in the present invention may contain an inorganic filler. The inorganic filler is not particularly limited, and for example, powders such as boron nitride, titanium oxide, talc, calcium carbonate, zinc oxide, clay, bentonant, molybdenum disulfide, silica, and graphite can be used. As the inorganic filler, boron nitride, titanium oxide, and graphite are preferable. These inorganic fillers may be used alone or in combination of two or more.
The content of the inorganic filler is not particularly limited, but when the saturated polyester resin is 100 parts by mass, it is preferably 15 parts by mass or less, particularly 12 parts by mass or less, and further preferably 10 parts by mass or less. By containing 1 to 15 parts by mass of an inorganic filler, for example, when used for adhesion of an adherend that is a circuit member made of metal, resin or the like, a circuit pattern or the like can be concealed.
The hot melt adhesive used in the present invention may further contain other additives. Examples of the additive include additives usually used in a hot melt adhesive composition, such as a stabilizer, an ultraviolet absorber and an antioxidant.

  The hot melt adhesive composition used in the present invention is prepared from a saturated polyester resin that contains the above-mentioned composition in various ways and has a specific storage elastic modulus (G ′), loss elastic modulus (G ″) and the like. For example, when the total amount of dicarboxylic acid residues is 100 mol%, the total amount of 55 mol% terephthalic acid, 30 mol% adipic acid, 15 mol% sebacic acid and diol residues is 100 mol%. %, 1,6-hexanediol, 7 mol% maleic acid, 3 mol% trimethylolpropane were copolymerized to prepare a saturated polyester resin, and the loss modulus ( G ″), and even if the composition is appropriately changed from the copolymer composition, the necessary characteristics can be easily adjusted by adjusting the conditions as shown below. . For example, when the loss elastic modulus (G ″) deviates to the larger one, the mass average molecular weight decreases, and when the loss elastic modulus (G ″) deviates to the smaller one, the mass average molecular weight increases. What is necessary is just to adjust copolymerization conditions. In order to obtain the loss elastic modulus (G ″) of the present invention by blending the above components, it can be obtained by adjusting the mass average molecular weight to about 20,000 to 35,000. Loss elastic modulus (G ′) Is not within the scope of the present invention, an inorganic filler such as titanium oxide, talc, calcium carbonate, silica, etc. is added, and monitoring is performed so that the storage elastic modulus (G ″) does not increase. When the loss elastic modulus (G ″) deviates in a direction larger than the range of the present invention, the polyfunctionality in the copolymer composition can be obtained. When such a saturated polyester resin is used, a hot melt contact having excellent initial adhesive strength, heat resistance, water resistance, etc. in addition to punchability is obtained. It can be a composition.

Next, the hot melt adhesive film laminate of the present invention will be described. The hot melt adhesive film laminate of the present invention is a laminate in which a carrier film made of a plastic film having a Young's modulus of 2 to 15 GPa is laminated on one side or both sides of the hot melt adhesive film of the present invention. Provided. When the Young's modulus of the plastic film is 2 to 15 GPa, when performing precision punching, the cutting property becomes good and the sagging can be reduced. The plastic film having a Young's modulus of 2 to 15 GPa is not particularly limited, but a polyester film is preferably used.
Examples of the polyester film used in the hot melt adhesive film laminate of the present invention include polyethylene terephthalate, polyethylene 2,6-naphthalate, polyethylene α, β-bis (2-chlorophenoxy) ethane 4,4′-dicarboxylate, A film made of polybutylene terephthalate or the like is preferable. Among these, a biaxially stretched film made of polyethylene terephthalate is particularly preferably used in consideration of mechanical properties, quality such as workability, and economical efficiency.

  The ratio of the thickness of the hot melt adhesive film to the thickness of the carrier film used in the hot melt adhesive film laminate of the present invention is preferably 0.2 to 1.0, and if it is 0.25 to 0.9 More preferably, 0.3 to 0.8 is even more preferable. Here, the thickness of the carrier film indicates the thickness of the carrier film on one side as it is when the carrier film is laminated on one side, but the thickness of the carrier film on both sides when laminated on both sides. Represents the sum of. When the thickness ratio is greater than 1.0, the percentage of the hot melt adhesive film occupied by the cut surface during precision punching increases, and as a result, the hot melt adhesive composition is formed on the side surfaces of the punch and / or die. It may adhere. When it is less than 0.2, the hot melt adhesive composition does not adhere to the side surfaces of the punch and / or die, but it is economically disadvantageous when used as a carrier. When it is 0.2 to 1.0, the hot melt adhesive composition does not adhere to the side surface of the punch and / or die, and it is economical and preferable.

  The method for producing the hot-melt adhesive film laminate of the present invention is not particularly limited, but the hot-melt adhesive composition is previously melted at a temperature equal to or higher than the melting point for the purpose of imparting film-forming properties and suitability for secondary processing, A method in which a hot melt adhesive composition is dissolved in an organic solvent to prepare a plastic prepared in advance by applying it on a carrier film made of a plastic film prepared in advance through a slit die and cooling and solidifying it. It can form by apply | coating on the carrier film which consists of a film, and drying and setting it as a coating film.

  The coating method of the coating solution is not particularly limited, and methods such as a gravure coating method, a reverse coating method, a kiss coating method, a die coating method, and a bar coating method can be used. The coating solution concentration, coating film drying conditions, or coating film cooling conditions are not particularly limited, but it is desirable that the coating film drying conditions be within a range that does not adversely affect various properties of the substrate.

  Moreover, in the hot melt adhesive film laminate of the present invention, the hot melt adhesive film is formed by making a film-like material in advance with the coating solution and sticking it to a carrier film made of a plastic film prepared in advance. Can do. When sticking, a method of applying a coating solution to a release film such as a silicone resin film and transferring it to a substrate is employed.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
Example 1
[Preparation of hot melt adhesive composition]
10 parts by weight of a linear low density polyethylene resin having a weight average molecular weight of 100,000 and 100 parts by weight of a saturated polyester resin having a weight average molecular weight of 30,000 having the composition shown in Table 1 and 1 part by weight of γ-glycidoxypropyltrimethoxysilane A hot melt adhesive composition A is prepared and is dynamically operated with a 20 mmφ cone plate, a GAP size of 1.0 mm, an amplitude sweep, a frequency of 1 Hz, and a stress auto mode using a rheometer “GEMINI 200HR NANO” manufactured by Bohlin. The viscoelasticity measurement was performed, and the storage elastic modulus (G ′) and loss elastic modulus (G ″) in the temperature region up to 150 ° C. were measured every 5 ° C. to 5 ° C. to obtain the graph of FIG.

[Method for creating hot melt adhesive film laminate]
A release film obtained by applying and drying a silicone release agent on one surface of a polyethylene terephthalate (PET) film “Lumirror” (registered trademark) (type S10) 38 μm (manufactured by Toray Industries, Inc.) was used as a carrier film. Moreover, 42 mass% solution which melt | dissolved hot melt adhesive composition A of the composition shown in Table 1 in toluene / MEK (methyl ethyl ketone) = 4/1 (mass ratio) was prepared as a coating liquid. 67 g / m ^{2 of} this coating solution is applied on one side of a carrier film with a comma coater and dried at 120 ° C. for 5 minutes to obtain a hot melt adhesive film laminate A-1 having a hot melt layer on one side of a PET substrate. It was. The thickness of the hot melt adhesive film layer was 20 μm.
[Punching method]
Using a punching machine FP-1213 manufactured by UHP Co., Ltd., using a punch with a size of 4.100 mm × 1.500 mm, R = 0.040 mm and a die with a size of 4.110 mm × 1.510 mm, While punching 4100mm x 1.500mm in size to Laminate A-1 is laterally moved at 3mm pitch, 2000 holes are punched at a rate of 100 shots per minute and attached to the punch and die after processing. Table 2 shows the results obtained by observing the adhesion of the hot-melt adhesive composition and the foreign matter adhesion state of the stamped test piece.
[Adhesive strength measurement method]
The carrier film is peeled from the prepared test piece, and a hot melt adhesive film and two polyethylene terephthalate (PET) films “Lumirror” (registered trademark) (type S10) 50 μm (manufactured by Toray Industries, Inc.) are PET / hot. The layers were stacked in the order of melt adhesive film / PET, and heat sealed under conditions of a temperature of 150 ° C., a pressure of 0.2 MPa, and a sealing time of 2 seconds to prepare a test piece for measuring adhesive strength.
Next, after leaving the test piece for measuring the adhesive force in a thermostatic chamber at 23 ° C. for 1 hour, using an autograph manufactured by Shimadzu Corporation, the two PET films were pinched and the adhesive force was adjusted at a peeling angle of 180 degrees and a peeling speed of 50 mm / min. The measurement was performed, and those having an adhesive strength of 3 N / cm or more were determined as “◯”, and those having an adhesive strength of less than 3 N / cm were determined as “X”.
(Example 2)
A hot melt having a 30 μm hot melt adhesive composition A on one side of a PET substrate in the same manner as in Example 1 except that the coating solution was applied at 100 g / m ^{2 on} one side of the carrier film and dried at 120 ° C. for 120 seconds. An adhesive film laminate A-2 was prepared and evaluated in the same manner as in Example 1.
(Example 3)
In the hot melt adhesive composition A, the terephthalic acid component was changed to 65 mol% and the sebacic acid component was changed to 5 mol% to obtain a mass average molecular weight of 28,000, and the storage elastic modulus (G ′) and loss elastic modulus ( G ″) was obtained. A hot melt adhesive composition B was obtained in the same manner as in Example 1 except that the hot melt adhesive composition A in Example 1 was replaced with the hot melt adhesive composition B. Body B-1 was prepared and evaluated similarly.
Example 4
3 parts by mass of titanium oxide as an inorganic filler is added to 100 parts by mass of the hot melt adhesive composition A, and the hot melt adhesive having the storage elastic modulus (G ′) and loss elastic modulus (G ″) shown in FIG. A composition C was obtained, in which the hot melt adhesive composition A of Example 1 was replaced with the hot melt adhesive composition C, and a hot melt adhesive film laminate C-1 was prepared in the same manner as in Example 1. Was evaluated.
(Example 5)
A release film obtained by applying and drying a silicone release agent on one surface of a polyethylene terephthalate (PET) film “Lumirror” (registered trademark) (type S10) 38 μm (manufactured by Toray Industries, Inc.) was used as a carrier film. A hot melt adhesive composition A melted at 230 ° C. was extruded onto this carrier film to form a 45 μm thick hot melt adhesive film layer, and a polyethylene terephthalate (PET) film “Lumirror” (registered trademark) (type E20). ) 100 μm (manufactured by Toray Industries, Inc.) was laminated to produce a hot melt adhesive film hot melt adhesive film laminate A-3, and the same evaluation as in Example 1 was performed.
(Comparative Example 1)
In the hot melt adhesive composition A of Example 1, the terephthalic acid component is changed to 85 mol%, the adipic acid component is changed to 20 mol%, and the sebacic acid component is changed to 0 mol% to obtain a mass average molecular weight of 100,000, which is shown in FIG. A hot melt adhesive composition D having a storage elastic modulus (G ′) and a loss elastic modulus (G ″) was obtained. The hot melt adhesive composition A of Example 1 was replaced with the hot melt adhesive composition D. The hot melt adhesive film laminate D-1 was prepared in the same manner as in Example 1, and the same evaluation was performed.
(Comparative Example 2)
A hot melt adhesive film laminate having a hot melt adhesive composition A of 55 μm on one side of a PET substrate, coated with 180 g / m ^{2 on} one side of the carrier film in the same manner as in Example 1 and dried at 120 ° C. for 5 minutes. A-4 was prepared and evaluated in the same manner as in Example 1.
(Comparative Example 3)
A hot melt adhesive film laminate A-5 having a hot melt adhesive composition A of 60 μm on one side of a 100 μm PET substrate was prepared in the same manner as in Example 5, and the same evaluation as in Example 1 was performed.
(Comparative Example 4)
The hot melt adhesive composition A of Example 1 was replaced with hot melt adhesive composition E having storage elastic modulus (G ′) and loss elastic modulus (G ″) shown in FIG. A melt-adhesive film laminate E-1 was prepared and evaluated in the same manner.

  As is clear from Table 2, the hot melt adhesive film laminates shown in Examples 1 to 5 were all continuous without the hot melt adhesive composition adhering to the side surfaces of the punch and die and without staining the test piece. Can be punched, and has sufficient adhesive strength. On the other hand, in the hot melt adhesive film laminates shown in Comparative Examples 1 to 3, the hot melt adhesive composition adhered to the side surfaces of the punch and the die or the test piece was soiled. Comparative Example 4 was able to obtain the same good results as in Examples in the punching process, but could not maintain a sufficient adhesive force to the adherend.

Claims (3)

The storage elastic modulus (G ′) in the temperature range of 10 ° C. to 40 ° C. including the saturated polyester resin is 1 × 10 ⁶ to 1 × 10 ¹⁰ Pa and the loss elastic modulus in the temperature range of 100 ° C. to 150 ° C. ( A hot melt adhesive film having a thickness of 5 to 50 μm, comprising a hot melt adhesive composition having G ″) of 1 × 10 ¹ to 1 × 10 ⁴ Pa. A hot melt adhesive film laminate comprising a plastic film having a Young's modulus of 2 to 15 GPa or more laminated on one side or both sides of the hot melt adhesive film according to claim 1. The hot melt adhesive film laminate according to claim 2, wherein the ratio of the thickness of the hot melt adhesive film to the thickness of the carrier film is 0.2 to 1.0.

Images