JP2019098620A - Manufacturing method of laminate and laminate - Google Patents

Abstract

To provide a manufacturing method of a laminate consisting of a substrate layer containing semi-aromatic polyamide and a polymer other than semi-aromatic polyamide such as polyolefin, good in layer adhesiveness, and especially having no reduction of adhesive force even when severe treatments under high temperature high humidity atmosphere or a warm water treatment or the like are conducted.SOLUTION: This invention relates to a manufacturing method of a laminate by laminating an adhesive layer (B) consisting of a polymer composition for adhesive (β) satisfying following (i) to (iii) on at least one surface of a substrate layer (A) consisting of a polymer (α) having a NH group at a molecule terminal. (i) it contains polyolefin formed by reacting polyolefin (a) having a group which reacts with a carbodiimide group, and a carbodiimide group-containing compound (b). (ii) it contains the carbodiimide group of 0.1 to 50 mmol based on 100 g of the polymer composition for adhesion. (iii) density is 0.870 g/cmto 0.940 g/cm.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a laminate having a base material layer comprising a polymer (α) having an NH group at a molecular terminal, and a laminate.

  Semi-aromatic polyamides containing aromatic dicarboxylic acid component units are significantly superior in heat resistance, mechanical properties and chemical physical properties as compared to aliphatic polyamides such as nylon 6, nylon 66, etc. It has been put to practical use as various component materials such as for electric and electronics, for industrial materials, for industrial materials, and for daily and household products.

  When semi-aromatic polyamide is used for various parts materials such as for automobiles, for electrics and electronics, for industrial materials, for industrial materials, for daily use and household goods, it is usually laminated with other resins, When laminating a semi-aromatic polyamide and another resin, in order to improve the interlayer adhesion, for example, grafting an unsaturated carboxylic acid or its derivative onto an ethylene / α-olefin copolymer as an adhesive layer It has been proposed to use an adhesive layer composed of a modified ethylene / α-olefin copolymer (Patent Document 1).

JP, 2015-231709, A

  The inventors of the present invention have studied a method for producing a laminate including a base material layer (A) comprising a polymer (α) having an NH group at a molecular terminal represented by a semi-aromatic polyamide. In order to improve the adhesive strength, the use of maleic anhydride graft modified polypropylene as an adhesive was examined. As a result, although the adhesion between the semi-aromatic polyamide layer and the maleic anhydride graft modified polypropylene layer is relatively good at room temperature or high temperature atmosphere, the adhesion is not always sufficient in the presence of water It has been found. In the case of contact with warm water, in particular, there is a problem that the adhesive strength decreases dramatically, and the adhesive strength decreases in pipe parts used under high temperature and high humidity atmosphere such as in the engine room of a car or for a long time outdoors In some cases, it has been found that the problem arises that the laminated layer peels off.

  The object of the present invention is to adhere a substrate layer (A) containing a semiaromatic polyamide or the like to a layer comprising a polymer other than a semiaromatic polyamide such as polyolefin, so that the adhesiveness is good, especially at high temperatures. It is an object of the present invention to provide a method for producing a laminate capable of easily producing a laminate in which the adhesive strength does not decrease even if severe treatment such as wet atmosphere treatment or warm water treatment is performed.

That is, the present invention relates to the following [1] to [8].
[1] Adhesion comprising an adhesive polymer composition (β) satisfying the following (i) to (iii) on at least one side of a base layer (A) consisting of a polymer (α) having an NH group at the molecular end The manufacturing method of the laminated body characterized by laminating | stacking layer (B).
(I) A polyolefin formed by the reaction of a polyolefin (a) having a group reactive with a carbodiimide group and a carbodiimide group-containing compound (b) is included.
(Ii) It contains a carbodiimide group in an amount of 0.1 to 50 mmol per 100 g of the adhesive polymer composition.
(Iii) a density of ^{0.870g / cm 3 ~0.940g / cm 3} .
[2] The polymer (α) and the weight on the side of the adhesive layer (B) comprising the adhesive polymer composition (β) on the side opposite to the side in contact with the layer (A) of the adhesive layer (B) The method for producing a laminate according to [1], wherein a layer (C) comprising a polymer (γ) different from any of the combined composition (β) is laminated on at least a part thereof.
[3] The method for producing a laminate according to [1] or [2], wherein the polymer (α) having an NH group at the molecular terminal includes a semiaromatic polyamide.
[4] The method for producing a laminate according to [3], wherein the semiaromatic polyamide is composed of a dicarboxylic acid component unit (c1) and a diamine component unit (c2).
[5] The method for producing a laminate according to [4], wherein the dicarboxylic acid component unit (c1) contains at least a terephthalic acid component unit.
[6] The method for producing a laminate according to any one of [2] to [5], wherein the polymer (γ) contains a polyolefin.
[7] After laminating the base material layer (A) and the adhesive layer (B) and optionally laminating the layer (C), retorting the obtained laminate in warm water The manufacturing method of the laminated body as described in any one of [1]-[6] characterized by the above-mentioned.
[8] An adhesive layer (B) comprising a base material layer (A) comprising a polymer (α) having an NH group at the molecular end, and an adhesive composition (β) at least a part of which is in contact with the layer (A) Including and
A laminate, wherein the adhesive composition (β) satisfies the following (i) to (iii).
(I) A polyolefin formed by the reaction of a polyolefin (a) having a group reactive with a carbodiimide group and a carbodiimide group-containing compound (b) is included.
(Ii) It contains a carbodiimide group in an amount of 0.1 to 50 mmol per 100 g of the adhesive composition (β).
(Iii) a density of ^{0.870g / cm 3 ~0.940g / cm 3} .

  According to the present invention, from a specific adhesive polymer composition (β) comprising a carbodiimide group-containing polyolefin, wherein a polyolefin (a) having a group that reacts with a carbodiimide group and a carbodiimide group-containing compound (b) react The laminate obtained by laminating the adhesive layer (B) and the base material layer (A) has a strong bond between the adhesive layer (B) and the base material layer (A). It is possible to obtain a laminate in which adhesion does not decrease even if severe treatment such as warm water treatment is performed.

  In addition, since the adhesive layer (B) is also excellent in adhesion to the layer (C) made of other polymers such as polyolefin, for example, severe treatment such as high temperature and high humidity atmosphere or warm water treatment is performed. Also, a laminate having no decrease in adhesion can be easily obtained.

Hereinafter, the present invention will be described in more detail.
[Base layer (A) comprising polymer (α) having NH group at molecular terminal]
In the base material layer (A) constituting the laminate according to the present invention, the polymer (α) having an NH group at the molecular end can be used without particular limitation as long as it has an NH group at the molecular end. In particular, semiaromatic polyamides are preferred. Moreover, as a preferable aspect of NH group of molecular terminal, NH ₂ group, NHR group and the like can be mentioned. Among these, an NH ₂ group is preferable from the viewpoint of easy availability.

Hereinafter, in the present invention, even if the group at the molecular end is an NH ₂ group or an NHR group, it is referred to as “polymer (α) having NH group at molecular end”. In addition, the NH group at the molecular terminal of polyamide is also described as an amino group.

  The semi-aromatic polyamide is a polymer containing a dicarboxylic acid component unit (c1) containing a terephthalic acid component unit and a diamine component unit (c2) containing an aliphatic diamine component unit having 4 to 20 carbon atoms.

The base material layer (A) according to the present invention may contain only one type of the semiaromatic polyamide, or may contain two or more types.
The melting point (Tm _A ) of the polymer (α) measured by differential scanning calorimetry (DSC) is 250 to 340 ° C., preferably 260 to 335 ° C., and more preferably 280 to 335 ° C. When the melting point of the polymer (α) is in the above range, the moldability of the base material layer (A) and the heat resistance of the laminate obtained from the base material layer (A) can be compatible.

When the polymer (α) is a semiaromatic polyamide, the melting point (Tm _A ) is the kind, molecular weight, etc. of the dicarboxylic acid component unit (c1) and the diamine component unit (c2) constituting the semiaromatic polyamide. Adjusted. When the polymer (alpha) comprises two or more semi-aromatic polyamide, the melting point (Tm _A) as measured by DSC mixtures thereof, it may be in the range.

  The glass transition temperature (Tg) of the polymer (α) measured by differential scanning calorimetry (DSC) is preferably 70 to 160 ° C., and more preferably 80 to 150 ° C. The heat resistance of the laminated body containing a base material layer (A) becomes high as the glass transition temperature (Tg) of a polymer ((alpha)) is the said range.

The melting point (Tm _A ) and the glass transition temperature (Tg) of the polymer (α) are measured by a differential scanning calorimeter (for example, model DSC 220C, manufactured by Seiko Instruments Inc.). Specifically, about 5 mg of the polymer (α) is sealed in an aluminum pan for measurement, and heated to 340 ° C. at room temperature to 10 ° C./min. In order to completely melt the polymer (α), the temperature is maintained at 340 ° C. for 5 minutes, and then it is cooled to 30 ° C. at 10 ° C./min. After 5 minutes at 30 ° C., a second heating to 340 ° C. is performed at 10 ° C./min. The peak temperature (° C.) at this second heating is taken as the melting point (Tm _A ) of the polymer (α), and the displacement point corresponding to the glass transition is taken as the glass transition temperature (Tg).

  Further, the intrinsic viscosity [η] of the polymer (α) measured in a 96.5% sulfuric acid at a temperature of 25 ° C. is preferably 0.4 to 3.0 dl / g, and 0.8 to 2.0 dl. It is more preferable that it is / g. When the limiting viscosity [η] of the polymer (α) is in the above range, the mechanical strength of the laminate obtained from the base material layer (A) tends to be sufficiently increased. On the other hand, when the intrinsic viscosity is in the above range, the flowability at the time of molding of the base material layer (A) is likely to be enhanced, and it becomes easy to mold in a desired shape. The above-mentioned intrinsic viscosity [η] is adjusted by the molecular weight of the polymer (α).

The above-mentioned intrinsic viscosity [η] is obtained by dissolving about 0.5 g of the polymer (α) in 50 ml of 96.5% concentrated sulfuric acid, and flowing the obtained solution under the conditions of 25 ° C. ± 0.05 ° C. The number is measured using a Ubbelohde viscometer, which is a value calculated based on the following equation.
[Η] = ηSP / (C (1 + 0.205ηSP))
In the above equation, each algebra or variable represents
[Η]: Intrinsic viscosity (dl / g)
ηSP: specific viscosity C: sample concentration (g / dl)
The above ηSP is obtained by the following equation.
ηSP = (t−t0) / t0
t: Seconds of flow of sample solution (seconds)
t0: Blank sulfuric acid flow down seconds (seconds)
Here, as described above, the polymer (α) is mainly composed of the dicarboxylic acid component unit (c1) and the diamine component unit (c2).

  The dicarboxylic acid component unit (c1) contains at least terephthalic acid component unit. The amount of the terephthalic acid component unit is preferably 20 to 100 mol%, more preferably 30 to 100 mol%, still more preferably 35 to 100 mol% relative to the total amount 100 mol% of the dicarboxylic acid component unit (c1). It is 100 mol%. When the dicarboxylic acid component unit (c1) contains 20% by mole or more of terephthalic acid component unit, the crystallinity of the polymer (α) is likely to be enhanced, and the heat resistance and the rigidity of the obtained laminate are likely to be enhanced.

  Furthermore, the dicarboxylic acid component unit (c1) may contain any one or both of an aromatic dicarboxylic acid component unit other than terephthalic acid and an aliphatic dicarboxylic acid component unit having 4 to 20 carbon atoms. Good. The amount of aromatic dicarboxylic acid component units other than terephthalic acid is preferably 0 to 80 mol%, more preferably 0 to 75 mol%, based on 100 mol% of the total amount of dicarboxylic acid component units (c1). More preferably, it is 0 to 70 mol%. When the dicarboxylic acid component unit (c1) contains an aromatic dicarboxylic acid component unit other than terephthalic acid, the impact resistance is improved. On the other hand, the amount of the aliphatic dicarboxylic acid component unit having 4 to 20 carbon atoms is preferably 0 to 60 mol%, more preferably 0 to 60 mol% with respect to 100 mol% of the total amount of dicarboxylic acid component units (c1). It is 58 mol%, more preferably 0 to 55 mol%. When the dicarboxylic acid component unit (c1) contains an aliphatic dicarboxylic acid component unit, the fluidity will be good.

  The aromatic dicarboxylic acid component unit other than terephthalic acid can be a component unit derived from an aromatic dicarboxylic acid compound having an aromatic ring and two carboxyl groups. Examples of aromatic dicarboxylic acid compounds include isophthalic acid, 2-methylterephthalic acid, naphthalene dicarboxylic acid and the like. The dicarboxylic acid component unit (c1) may contain only one type of aromatic dicarboxylic acid component unit other than terephthalic acid, or may contain two or more types. The aromatic dicarboxylic acid component unit other than terephthalic acid is preferably an isophthalic acid component unit.

  On the other hand, the aliphatic dicarboxylic acid component unit having 4 to 20 carbon atoms can be a component unit derived from an aliphatic dicarboxylic acid compound having an aliphatic chain having 4 to 20 carbon atoms and two carboxyl groups. . Examples of aliphatic dicarboxylic acid compounds include dimethyl malonic acid, succinic acid, glutaric acid, adipic acid, 2-methyl adipic acid, trimethyl adipic acid, pimelic acid, 2,2-dimethyl glutaric acid, 3,3-diethyl succinic acid The acid, azelaic acid, sebacic acid, suberic acid, and aliphatic dicarboxylic acids having 11 or more carbon atoms are included. The dicarboxylic acid component unit (c1) may contain only one type of aliphatic dicarboxylic acid component unit, or may contain two or more types. The aliphatic dicarboxylic acid component unit is preferably an adipic acid component unit.

  The dicarboxylic acid component unit (c1) may contain an alicyclic dicarboxylic acid component unit as long as the effects of the present invention are not impaired. Examples of alicyclic dicarboxylic acid component units include furandicarboxylic acids such as 2,5-furandicarboxylic acid, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid, and the like. Be

  Here, the dicarboxylic acid component unit (c1) preferably contains a terephthalic acid component unit and an isophthalic acid component unit. In this case, the molar ratio of terephthalic acid component unit to isophthalic acid component unit is preferably 60/40 to 99.9 / 0.1, more preferably 60/40 to 90/10, and 60 It is further more preferable that it is / 40-85 / 15. When the amount of the terephthalic acid component unit is in the above range, the heat resistance and the rigidity of the laminate obtained from the base material layer (A) are likely to be enhanced. On the other hand, when the amount of isophthalic acid component units is in the above range, the fluidity can be easily improved while maintaining the rigidity.

  The dicarboxylic acid component unit (c1) also preferably contains a terephthalic acid component unit and an adipic acid component unit. In this case, it is preferable that 40 to 80 mol% of terephthalic acid component unit and 20 to 60 mol% of adipic acid component unit are contained with respect to 100 mol% of the total amount of the dicarboxylic acid component unit (c1).

  On the other hand, the diamine component unit (c2) contains at least an aliphatic diamine component unit having 4 to 20 carbon atoms. The amount of the aliphatic diamine component unit is preferably 30 to 100 mol%, more preferably 35 to 100 mol%, based on 100 mol% of the total amount of diamine component units (c2). More preferably, it is 100 mol%. When the amount of the aliphatic diamine component unit is in the above range, the flowability is likely to be enhanced, and the impact resistance of the laminate is likely to be enhanced.

  Here, the carbon atom number in the aliphatic diamine component unit is preferably 4 to 15, more preferably 4 to 13, and particularly preferably 6 to 12. When the number of carbon atoms of the aliphatic diamine component unit is 4 or more, the hygroscopicity and water absorption of the resulting molded article become low, and deterioration with time and the like is easily suppressed.

  The aliphatic diamine component unit is a component unit derived from a linear alkylene diamine compound (hereinafter, also referred to as “a linear alkylene diamine component unit”), or a component unit derived from an alkylene diamine compound having a side chain (hereinafter referred to as “side It is preferable to include at least one or both of chain alkylene diamine component units). The number of carbon atoms of the side chain alkylene diamine is the number including the number of carbon atoms contained in the side chain.

  Here, it is preferable that a diamine component unit (c2) contains 40 mol% or more of a linear alkylene diamine component unit with respect to 100 mol% of the total amount. When the linear alkylene diamine component unit is contained in a certain amount or more, the water resistance of the polymer composition tends to be enhanced. On the other hand, it is preferable that an aliphatic diamine component unit contains 3-60 mol% of side chain alkylene diamine component units with respect to the total amount 100 mol%. When the aliphatic diamine component unit contains a certain amount of side chain alkylene diamine component unit, the high temperature rigidity of the resulting molded article is likely to be enhanced.

  Examples of linear alkylene diamine compounds include 1,4-butanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10- Included are decane diamine, 1,11-undecane diamine, 1,12-dodecane diamine and the like. The diamine component unit (c2) may contain only 1 type of linear alkylene diamine component unit, and may contain 2 or more types. Among these, 1,6-hexanediamine and 1,9-nonanediamine are preferable, and it is preferable that the total amount of these is 50 to 100 mol% with respect to 100 mol% of the total amount of linear alkylene diamine, and 80 It is more preferable that the amount is 100 to 100 mol%.

  Examples of the alkylenediamine compound having a side chain include 2-methyl-1,5-pentanediamine, 2-methyl-1,6-hexanediamine, 2-methyl-1,7-heptanediamine, 2-methyl-1 , 8-octanediamine, 2-methyl-1,9-nonanediamine, 2-methyl-1,10-decanediamine, 2-methyl-1,11-undecanediamine and the like. The diamine component unit (c2) may contain only one type of side chain alkylene diamine component unit, or may contain two or more types. Among these, 2-methyl-1,5-pentanediamine and 2-methyl-1,8-octanediamine are preferable.

  When the diamine component unit (c2) contains both a linear alkylene diamine component unit and a side chain alkylene diamine component unit, as an example of a preferable combination thereof, 1,6-diaminohexane component unit and 2-methyl-1 A combination with a 5-pentadiamine component unit is mentioned. At this time, 1,6-diaminohexane component unit is more than 45 mol% and less than 55 mol% with respect to 100 mol% of the total amount of diamine component units (c2), and 2-methyl-1,5-pentadiamine is More than 45 mol% and less than 55 mol% is preferable. Moreover, the combination of a 1, 9- nonane diamine component unit and a 2-methyl- 1, 8- octane diamine component unit is also mentioned as another example of a preferable combination. At this time, 1,9-nonane diamine component unit is more than 45 mol% and less than 85 mol% with respect to 100 mol% of the total amount of diamine component units (c2), and 2-methyl-1,8-octane diamine component unit Is preferably more than 15% by mole and less than 55% by mole.

  The diamine component unit (c2) contains an aliphatic diamine component unit having a larger number of carbon atoms than the above aliphatic diamine component unit (4 to 20 carbon atoms), as long as the effects of the present invention are not impaired. It is also good. The diamine component unit (c2) may contain an alicyclic diamine component unit or an aromatic diamine component unit. Examples of the alicyclic diamine component unit include component units derived from an alicyclic diamine compound having 4 to 15 carbon atoms. Examples of alicyclic diamine compounds include 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, isophorone diamine, piperazine 2,5-Dimethylpiperazine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, 4,4'-diamino-3,3'-dimethyldicyclohexylpropane, 4,4'-diamino-3 , 3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-dimethyldicyclohexylmethane and the like. Among them, alicyclic diamine component units are 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 4,4′-diamino-3,3 Component units derived from '-dimethyldicyclohexylmethane are preferred, in particular 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 1,3-bis (aminocyclohexyl) methane, Component units derived from 1,3-bis (aminomethyl) cyclohexane are preferred. The total amount of aliphatic diamine component units having a large number of carbon atoms, aromatic diamine component units, and alicyclic diamine component units is 5 mol% or less based on 100 mol% of the total amount of diamine component units (c2) Being particularly preferred.

  As an example of a polymer particularly preferable as the polymer (α), the dicarboxylic acid component unit (c1) is a terephthalic acid component unit, and the diamine component unit (c2) is 1,6-hexanediamine and 2-methyl- A polymer which is 1,5-pentanediamine; a dicarboxylic acid component unit (c1) is a terephthalic acid component unit, and a diamine component unit (c2) is 1,9-nonanediamine and 2-methyl-1,8-octane A polymer which is a diamine; a polymer wherein the dicarboxylic acid component unit (c1) is a terephthalic acid component unit and an isophthalic acid component unit, and the diamine component unit (c2) is 1,6-hexanediamine; a dicarboxylic acid component unit (C1) is a terephthalic acid component unit and an adipic acid component unit, and the diamine component unit (c2) is 1,6-hexanediamine There polymers, and the like. The base material layer (A) concerning this invention may contain only 1 type of these polymers ((alpha)), and may contain 2 or more types.

  Here, the polymer (α) may be sealed by an end capping agent. The end capping agent may be, for example, a monocarboxylic acid and a monoamine. By capping the carboxyl group and / or amino group at the end of the polymer (α) with the end capping agent, the amount of carboxyl groups and the amount of amino groups possessed by the polymer (α) are adjusted.

  The terminal amino group amount of the molecular chain of the polymer (α) is preferably 0.1 to 300 mmol / kg, more preferably 0.1 to 175 mmol / kg, and particularly preferably 0.1 to 150 mmol / kg. It is.

  On the other hand, when the amount of terminal amino groups is too large, the hygroscopicity and water absorption of molded articles tend to increase, but if the amount of terminal amino groups is 300 mmol / kg or less, a polymer having an NH group at the molecular terminal (α) Water absorption rate is low.

  The amount of terminal amino groups of the polymer (α) is adjusted by the ratio of diamine to dicarboxylic acid used in preparation of the polymer (α) having an NH group at the molecular terminal, and the amount of the end capping agent. For example, an end capping agent consisting of monocarboxylic acid or the like is added to a system containing diamine and dicarboxylic acid at the time of preparation of the polymer (α), and a part of the ends is capped to adjust the amount of terminal amino groups Ru.

The amount of terminal amino groups is measured by the following method. 1 g of the polymer (α) is dissolved in 35 mL of phenol, and 2 mL of methanol is mixed to prepare a sample solution. Then, titration using 0.01 N HCl aqueous solution is performed on the sample solution with thymol blue as an indicator, and the amount of terminal amino groups ([NH ₂ ], unit: mmol / kg) is specified.

  The polymer (α) can be produced in the same manner as a known polyamide, and can be produced, for example, by polycondensation of a dicarboxylic acid and a diamine in a uniform solution. More specifically, a lower condensate is obtained by heating a dicarboxylic acid and a diamine in the presence of a catalyst as described in WO 03/085029, and then this lower condensate It can be produced by polycondensation by applying shear stress to the melt of

  Moreover, when adjusting the intrinsic viscosity [[] of the polymer (α), a compound for adjusting the molecular weight (hereinafter, also referred to as “molecular weight modifier”) such as the above-mentioned terminal blocking agent is added to the reaction system. It is preferable to mix | blend. Molecular weight regulators can be, for example, monocarboxylic acids and monoamines. Examples of monocarboxylic acids which may be molecular weight modifiers include aliphatic monocarboxylic acids having 2 to 30 carbon atoms, aromatic monocarboxylic acids and alicyclic monocarboxylic acids. According to these molecular weight modifiers, while adjusting the molecular weight of a polymer ((alpha)), the quantity of the terminal amino group of a polymer ((alpha)) can be adjusted. The aromatic monocarboxylic acid and the alicyclic monocarboxylic acid may have a substituent at the cyclic structure portion.

  Examples of the above aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, oleic acid and linoleic acid Is included. Examples of the aromatic monocarboxylic acid include benzoic acid, toluic acid, naphthalene carboxylic acid, methyl naphthalene carboxylic acid, phenylacetic acid and the like, and examples of the alicyclic monocarboxylic acid include cyclohexane carboxylic acid and the like. Be

  The molecular weight modifier is added to the reaction system of dicarboxylic acid and diamine. The addition amount is preferably 0.07 mol or less, more preferably 0.05 mol or less, per 1 mol of the total amount of the dicarboxylic acid. By using a molecular weight modifier in such an amount, at least a portion thereof is incorporated into the polyamide, whereby the molecular weight of the polymer (α), that is, the intrinsic viscosity [η] is adjusted within the desired range. .

[Adhesive layer (B) consisting of polymer composition for adhesion (β)]
The adhesive layer (B) constituting the laminate according to the present invention comprises an adhesive polymer composition (β) satisfying the following requirements (i) to (iii).

(I) The adhesive polymer composition (β) includes a polyolefin formed by the reaction of a polyolefin (a) having a group that reacts with a carbodiimide group and a carbodiimide group-containing compound (b).
That is, the adhesive polymer composition (β) contains a polyolefin having a carbodiimide group.

[Polyolefin (a)]
The polyolefin (a) can be obtained by introducing a compound (m) having a group that reacts with a carbodiimide group into the polyolefin. The polyolefin (a) may be used alone or in combination of two or more.

  As a compound (m) which has a group which reacts with a carbodiimide group, the compound which has a group which has an active hydrogen which has reactivity with a carbodiimide group is mentioned. Specifically, compounds having a group derived from a carboxylic acid, an amine, an alcohol, a thiol and the like can be mentioned. Among these, compounds having a group derived from a carboxylic acid are suitably used, and among them, unsaturated carboxylic acids and / or their derivatives are particularly preferable. In addition to compounds having a group having active hydrogen, compounds having a group which is easily converted to a group having active hydrogen by water or the like can also be preferably used. Specifically, compounds having an epoxy group or glycidyl group can be mentioned.

The compound (m) having a group that reacts with a carbodiimide group may be used alone or in combination of two or more.
The unsaturated carboxylic acid and / or derivative thereof used as the compound (m) having a group reactive with a carbodiimide group is an unsaturated compound having one or more carboxylic acid groups, preferably one or more carboxylic acid anhydride groups The unsaturated compound which it has, and its derivative can be mentioned. Examples of unsaturated groups include vinyl, vinylene and unsaturated cyclic hydrocarbon groups. Specific compounds include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept-2 And unsaturated carboxylic acids such as -ene-5,6-dicarboxylic acid, or acid anhydrides thereof or derivatives thereof (for example, acid halides, amides, imides, esters, etc.). Specific examples of the compound include malenyl chloride, malenyl imide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid Anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconate, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5,6 Dimethyl dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate, aminopropyl methacrylate and the like can be mentioned.

  When using unsaturated carboxylic acid and / or its derivative as compound (m) which has a group which reacts with a carbodiimide group, it can also be used individually by 1 type, and can also be used combining 2 or more types. it can. Among these, maleic anhydride, (meth) acrylic acid, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride Preferred are hydroxyethyl (meth) acrylate, glycidyl methacrylate and aminopropyl methacrylate. Furthermore, dicarboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid anhydride are particularly preferred. preferable.

As a method for introducing a compound (m) having a group that reacts with a carbodiimide group into a polyolefin, a known method can be adopted. For example, a compound having a group that reacts with a carbodiimide group in a polyolefin main chain ( Examples thereof include a method of graft copolymerization of m) and a method of radical copolymerization of an olefin and a compound (m) having a group capable of reacting with a carbodiimide group.
Hereinafter, the case of graft copolymerization and the case of radical copolymerization will be separately described specifically.

<Graft copolymerization>
The polyolefin (a) having a group that reacts with a carbodiimide group can be obtained by graft copolymerization of a compound (m) having a group that reacts with a carbodiimide group on the polyolefin main chain.

(Polyolefin main chain)
The polyolefin used as the polyolefin main chain is a polymer having an aliphatic α-olefin having 2 to 20 carbon atoms, a cyclic olefin, or a nonconjugated diene as a main component, preferably an aliphatic α-olefin having 2 to 10 carbon atoms And, more preferably, polymers having 2 to 8 aliphatic α-olefins as a main component. These olefins may be used alone or in combination of two or more. In the case of a copolymer, the content of olefin as a comonomer is not particularly limited as long as the effects of the present invention can be obtained, but it is usually 50 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less It is. Among the polyolefins in such a range, crystalline polyolefins such as polyethylene, polypropylene, poly 1-butene, poly 4-methyl 1-pentene and α-olefin copolymers thereof are preferable, and polyethylene, polypropylene or propylene is preferable. Ethylene copolymers are more preferred. Moreover, these can be used in both an isotactic structure and a syndiotactic structure, and there is no particular limitation on the stereoregularity.

The density of the polyolefin used for graft modification (measured according to JIS K7112) is not particularly limited as long as the effects of the present invention can be obtained, but it is usually 0.8 to 1.10 g / cm ³ , preferably 0.8 to 1. It is .05 g / cm ³ , more preferably 0.8 to 1.00 g / cm ³ . The melt flow rate (MFR) at 230 ° C. under a load of 2.16 kg according to ASTM D1238 is not particularly limited as long as the effects of the present invention can be obtained, but it is usually 0.01 to 500 g / 10 min, preferably 0.05 to 200 g / min. It is preferably 10 minutes, more preferably 0.1 to 100 g / 10 minutes. If the density and MFR are in this range, the density of the graft copolymer after modification and the MFR will be comparable, and handling is easy.

  The crystallinity of the polyolefin used for graft modification is not particularly limited as long as the effects of the present invention can be obtained, but it is usually 2% or more, preferably 5% or more, and more preferably 10% or more. When the crystallinity degree is in this range, the handling of the graft copolymer after modification is excellent.

  The number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the polyolefin used for graft modification is preferably 5,000 to 500,000, and more preferably 10,000 to 100,000. When the number average molecular weight (Mn) is in this range, the handling is excellent. In the ethylene-based polyolefin, the number average molecular weight is determined in terms of polyethylene when the amount of comonomer is 10 mol% or less, and in ethylene-propylene when it is 10 mol% or more (based on 70 mol% of ethylene content). It is possible.

  The production of the above-mentioned polyolefin can be carried out by any known method, and for example, it can be polymerized using a titanium-based catalyst, a vanadium-based catalyst, a metallocene catalyst or the like. Further, the polyolefin used for graft modification may be any form of resin and elastomer, and both of isotactic structure and syndiotactic structure can be used, and there is no particular limitation on stereoregularity. It is also possible to use commercially available polymers as they are.

(Graft polymerization method)
When the polyolefin (a) having a group reactive with a carbodiimide group is obtained by graft copolymerization, a compound (m) having a group reactive with a carbodiimide group is further added to the above-mentioned polyolefin serving as the graft main chain, The other ethylenically unsaturated monomer etc. is graft copolymerized in the presence of a radical initiator.

  The method for grafting the compound (m) having a group that reacts with a carbodiimide group to the polyolefin main chain is not particularly limited, and conventionally known graft polymerization methods such as a solution method and a melt-kneading method can be adopted.

The graft amount of the compound (m) having a group that reacts with a carbodiimide group is usually 0.05 to 20% by weight, preferably 0.05 to 10% by weight, based on 100% by weight of the polyolefin (a). Preferably it is 0.05-5 weight%, More preferably, it is 0.05-3 weight%. The grafting amount of the compound (m) is a net grafting amount measured after removing the free compound (m) from the polyolefin (a). Further, the grafting amount can be measured by a known means such as ¹³ C-NMR or ¹ H-NMR measurement. In addition, when a monomer having an acidic functional group such as unsaturated carboxylic acid and its anhydride is used as the compound (m), an amount serving as a measure of the amount of the functional group introduced to the polyolefin (a) may be, for example It is also possible to use an acid value. When maleic anhydride is used, the amount of grafting can also be determined using an infrared spectrophotometer, based on the absorption spectrum of the carbonyl group of maleic anhydride which is usually detected in the vicinity of 1780 to 1790 cm ^-1. .

<Radical copolymerization>
The polyolefin (a) having a group that reacts with a carbodiimide group can also be obtained by radical copolymerization of an olefin and a compound (m) having a group that reacts with a carbodiimide group. As the olefin, it is possible to adopt the same one as the olefin in the case of forming the above-mentioned polyolefin to be a graft main chain, and the compound (m) having a group which reacts with a carbodiimide group is also as described above. is there.

The method for copolymerizing the olefin and the compound (m) having a group that reacts with a carbodiimide group is not particularly limited, and a conventionally known radical copolymerization method can be employed.
The content of the compound (m) residue having a group that reacts with a carbodiimide group in the polyolefin (a) that has a group that reacts with a carbodiimide group is usually 0.1 to 10% by weight, preferably 0.1 to 8 The content is 0.1% by weight, more preferably 0.1 to 6.0% by weight. If the content of the compound (m) residue having a group that reacts with a carbodiimide group is within the above range, the polyolefin (a) is suitably crosslinked with the carbodiimide group-containing compound (b), and the adhesive polymer composition It is preferable because (β) can be produced.

Further, the density (measured according to JIS K7112) of the polyolefin (a) having a group that reacts with a carbodiimide group is usually 0.870 to 0.940 g / cm ³ , preferably 0.875 to 0.940 g / cm. ^3, more preferably from 0.880g~0.940 / cm ^3.

(Carbodiimide-containing compound (b))
The carbodiimide group-containing compound (b) is a polycarbodiimide having a repeating unit represented by the following general formula (1). The carbodiimide group-containing compound (b) may be used alone or in combination of two or more.
-N = C = N-R ₁ ... (1)
[Wherein, R ₁ represents a divalent organic group having 2 to 40 carbon atoms. ]

  The polycarbodiimide can be produced by decarboxylation condensation reaction of an organic diisocyanate such as aliphatic diisocyanate, aromatic diisocyanate and alicyclic diisocyanate in the presence of a condensation catalyst in the absence of solvent or in an inert solvent. For example, hexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, xylylene diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, Diisocyanate such as isophorone diisocyanate is used alone or in combination. In the decarboxylation condensation reaction, the polymerization degree of polycarbodiimide can be controlled by selecting a catalyst, reaction temperature, end capping agent and the like. The polymerization degree is usually 2 to 40, preferably 4 to 20. As the end capping agent, monoisocyanate such as phenyl isocyanate, tolyl isocyanate and naphthyl isocyanate, and active hydrogen compounds such as methanol, ethanol, diethylamine, cyclohexylamine, succinic acid, benzoic acid and ethyl mercaptan can be used. As condensation catalysts, alcoholates such as titanium, hafnium, zirconium, sodium and calcium, and organic phosphorus compounds such as phosphalene oxide can be used.

  The polystyrene equivalent number average molecular weight (Mn) determined by gel permeation chromatography (GPC) of the carbodiimide group-containing compound (b) is not particularly limited as long as the effects of the present invention can be obtained, but it is usually 400 to 500,000, preferably Is from 700 to 10,000, more preferably from 1,000 to 8,000. When the number average molecular weight (Mn) is in this range, it is preferable because the adhesion of the adhesive polymer composition (β) is excellent.

The carbodiimide group-containing compound (b) may contain monocarbodiimide in polycarbodiimide, and it is also possible to use it alone or in combination of a plurality of compounds.
As the carbodiimide group-containing compound (b), it is also possible to use a commercially available carbodiimide group-containing compound as it is. Examples of commercially available carbodiimide group-containing compounds include Carbodilite (registered trademark) HMV-8CA and HMV-15CA manufactured by Nisshinbo Chemical Co., Ltd., and Carbodilite (registered trademark) LA1.

  As the number of carbodiimide groups in one carbodiimide compound molecule increases, the number of reaction points with the polymer (α) in one adhesive agent increases, so that the adhesive can be more firmly adhered to the base layer (A) made of the polymer (α) it can. From this, the number of carbodiimide groups in one molecule of the carbodiimide group-containing compound (b) is preferably 10 or more. The upper limit of the number of carbodiimide groups in one molecule of the carbodiimide group-containing compound (b) is not particularly limited as long as the effects of the present invention can be obtained, but when the number of carbodiimide groups in one molecule increases, the amount of addition of carbodiimide compound increases. Because the cost of raw materials increases, it is usually 30 in consideration of the cost.

The carbodiimide group content in the carbodiimide group-containing compound (b) can be measured by ¹³ C-NMR, IR, titration method or the like, and can be grasped as a carbodiimide group equivalent. It is possible to observe a peak attributed to a carbodiimide group at 130 to 142 ppm in ¹³ C-NMR and 2130 to 2140 cm ⁻¹ in IR.

^{The 13} C-NMR measurement is performed, for example, as follows. That is, 0.35 g of a sample is heated and dissolved in 2.0 ml of hexachlorobutadiene. The solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added, and the mixture is charged into an NMR tube with an inner diameter of 10 mm. Then, ¹³ C-NMR measurement is performed at 120 ° C. using a GX-500 NMR analyzer manufactured by Nippon Denshi Co., Ltd. The number of integrations is 10,000 or more.

(Reaction of Polyolefin (a) Having a Group Reactive with Carbodiimide Group and Compound (b) Containing Carbodiimide Group)
The polyolefin having a carbodiimide group contained in the adhesive polymer composition (β) preferably has a polyolefin (a) having a group that reacts with a carbodiimide group and a carbodiimide group-containing compound (b) at 230 ° C. or higher It is obtained by reacting. Specifically, the polymer composition for adhesion (β) can be obtained by melt-kneading as in melt modification, but is not limited to this method.

  Below, the example in the case of melt-mixing is shown. The method of reacting the polyolefin (a) having a group that reacts with a carbodiimide group with the carbodiimide group-containing compound (b), preferably at 230 ° C. or higher, is not particularly limited, but a group that reacts with a carbodiimide group A single-screw extruder, a multi-screw extruder, a kneader, for example, after charging and kneading the polyolefin (a) having the compound and the carbodiimide group-containing compound (b) in a Henschel mixer, V-type blender, V-type blender, tumbler blender, ribbon blender etc The method of melt-kneading with a Banbury mixer etc. can be illustrated. Among these, using an apparatus having excellent kneading performance such as a multi-screw extruder, a kneader, a Banbury mixer, etc., it is possible to obtain an adhesive polymer composition (β) in which each component is more uniformly dispersed and reacted. It is preferable because it can be done.

  The polyolefin (a) having a group that reacts with carbodiimide group and the carbodiimide group-containing compound (b) are mixed in advance and then supplied from a hopper, and some components are supplied from a hopper and extruded from near the hopper part It is possible to take any method of supplying other components from the supply port installed in any part between the tip of the machine.

  The temperature at the time of melt-kneading each of the above components can be the highest melting point or higher of the melting points of the respective components to be mixed, but specifically it is usually 180 to 320 ° C., preferably 230 to 300 ° C. More preferably, melt kneading is performed in the range of 235 to 280 ° C.

Moreover, the reaction rate of polyolefin (a) and a carbodiimide group containing compound (b) can be evaluated by the following method.
After preparing each heat press sheet for the adhesive polymer composition (β) containing the polyolefin (a) (reference) having a group that reacts with the carbodiimide group and the polyolefin having a carbodiimide group, red Infrared absorption is measured using an external absorption analyzer. From the obtained chart, the absorbance derived from the group that reacts with the carbodiimide group in the polyolefin (a), the absorbance derived from the group that reacts with the carbodiimide group in the polyolefin (a), and the polymer composition for adhesion The reaction rate can be calculated using the following formula (2) by comparing the difference in absorbance derived from the group that reacts with the carbodiimide group in (β). In addition, when using a maleic anhydride as group which reacts with a carbodiimide group, the light absorbency of 1790 cm < ^-1 > vicinity can be used.
Reaction rate (%) = {X / Y} × 100 (2)
X: Difference between the absorbance derived from the group that reacts with the carbodiimide group in the polyolefin (a) and the absorbance derived from the group that reacts with the carbodiimide group in the adhesive polymer composition Y: The carbodiimide group in the polyolefin (a) Absorbance derived from the group that reacts with

  The reaction rate determined by the above method for the adhesive polymer composition (β) is usually in the range of 40 to 100%, preferably 60 to 100%, and more preferably 80 to 100%.

(Ii) A carbodiimide group is contained in an amount of 0.1 to 50 mmol per 100 g of the adhesive polymer composition (β).
The adhesive polymer composition (β) contains a polyolefin having a carbodiimide group, and the amount of the carbodiimide group is 0.1 to 50 mmol per 100 g of the adhesive polymer composition (β), preferably 0. It is 2 to 40 mmol, more preferably 0.5 to 30 mmol. When the amount of carbodiimide groups in the adhesive polymer composition (β) is within the above range, the adhesive polymer composition (β) is excellent in adhesiveness and suppresses the crosslinking of the polyolefin (a). It is preferable because it can be done.

The content of the carbodiimide group in the adhesive polymer composition (β) can be measured by ¹³ C-NMR, IR, titration method or the like, and can be grasped as a carbodiimide group equivalent. It is possible to observe a peak attributed to a carbodiimide group at 130 to 142 ppm in ¹³ C-NMR and 2130 to 2140 cm ⁻¹ in IR. In addition, ¹³ C-NMR measurement is performed by, for example, the measurement method described in the carbodiimide group content in the above-mentioned carbodiimide group-containing compound (b) and the measurement method described in the examples.

  The adhesive polymer composition (β) is produced by reacting the carbodiimide group (NCN) of the polycarbodiimide with the compound (m) having a group that reacts with the carbodiimide group as described above, but the process of the reaction A certain amount of carbodiimide groups are consumed, and the residue of the carbodiimide group linked as a molecular chain with the polyolefin group contributes to the adhesion to the polymer (α) having an NH group at the molecular terminal. If the content of the carbodiimide group exceeds the above range, an excess of free carbodiimide group will be present with respect to the polyolefin (a) having a group that reacts with the carbodiimide group, and the adhesion performance and the molding processability will decrease.

(Iii) the density of the bonding polymer composition (beta) is ^{0.870g / cm 3 ~0.940g / cm 3} .
The density of the adhesive polymer composition (β) measured according to JIS K7112 is 0.870 to 0.940 g / cm ³ , preferably 0.875 to 0.940 g / cm ³ , and more preferably Preferably it is 0.880 g-0.940 / cm < ³ >. When the density of the adhesive polymer composition (β) is in the above-mentioned range, it is preferable because the stability productivity, the molding processability and the adhesiveness of the adhesive polymer composition (β) are good.

  The melt flow rate (MFR, according to ASTM D1238, 230 ° C., 2.16 kg load) of the adhesive polymer composition (β) is not particularly limited as long as the effects of the present invention can be obtained, but usually 0.01 to 500 g It is 10 minutes, preferably 0.05 to 200 g / 10 minutes, and more preferably 0.01 to 150/10 minutes.

  In addition, although a carbodiimide group changes to a urea group by water absorption, the urea group also exhibits high reactivity with a semi-aromatic polyamide. Therefore, the adhesive polymer composition (β) according to the present invention may contain, for example, a polyolefin in which the carbodiimide group is converted to a urea group by water or the like in the atmosphere, the present invention It is one of the preferred embodiments of

  For the adhesive polymer composition (β), a polyolefin (a) having a group that reacts with a carbodiimide group is used, but a polyolefin different from the polyolefin (a) such as non-modified polyolefin within a range not impairing the object of the present invention May be included. In addition, it is also possible to blend a modified polymer having a group that reacts with a carbodiimide group, which is different from the polyolefin (a) and the polyolefin having a carbodiimide group. As such a polymer, for example, a maleic acid-modified polymer and an imine-modified polymer can be mentioned. Among these, maleic acid-modified ethylene / butene copolymer, maleic acid-modified ethylene / propylene copolymer, maleic acid-modified ethylene / octene copolymer, maleic acid-modified styrene / butene / styrene copolymer, maleic acid-modified styrene Ethylene / butene / styrene copolymer, imine-modified styrene / butene / styrene copolymer, imine-modified styrene / ethylene / butene / styrene copolymer are preferable. These polymers may be used alone or in combination of two or more.

  Further, it is also possible to add known additives used in the field of polyolefin, for example, tackifiers, process stabilizers, heat stabilizers, heat aging agents, fillers, etc., to the polymer composition for adhesion (β). It is possible. In the present invention, it is particularly preferable to blend a tackifier for the purpose of imparting tackiness. Examples of tackifiers include rosin derivatives, terpene resins, petroleum resins, and hydrides thereof, and among these, hydrogenated terpene resins and hydrogenated petroleum resins are preferred. The tackifier is not particularly limited as long as the effects of the present invention can be obtained. For example, the tackifier may be blended in a ratio of 0 to 30% by weight with respect to 100% by weight of the adhesive polymer composition (β). Is preferred.

[Layer (C) comprising polymer (γ)]
The layer (C) which may constitute the laminate according to the present invention comprises a polymer (γ) which is different from any of the polymer (α) and the polymer composition for adhesion (β). The polymer (γ) is not particularly limited as long as the effects of the present invention are exhibited, but polyolefins, polylactic acids, polyketones, polyesters, polyamides, ethylene / vinyl alcohol copolymers and the like can be mentioned. The polymers (γ) may be used alone or in combination of two or more.

(Polyolefin layer)
It is preferred to use a polyolefin layer as a layer (C) which constitutes a layered product concerning the present invention.
The polyolefin layer comprises a polyolefin. Examples of the polyolefin include homopolymers and copolymers of an α-olefin having 2 to 20 carbon atoms. The polyolefin may be used alone or in combination of two or more. Specific examples of the α-olefin include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like. Further, the polyolefin may be copolymerized with a small amount, for example, 10 mol% or less, of another monomer other than the α-olefin. The other monomer is not particularly limited, but includes, for example, a monomer having a polar group (for example, a carbonyl group, a hydroxyl group, an ether bond group and the like) and a polymerizable carbon / carbon double bond in the molecule.

  Specific examples of the polyolefin include, for example, (1) ethylene homopolymer (the manufacturing method may be either low pressure method or high pressure method), (2) 99 to 80 mol% of ethylene and 1 to 20 mol% of propylene Ethylene-propylene copolymer, preferably ethylene-propylene copolymer of 95 to 85 mol% of ethylene and 5 to 15 mol% of propylene, (3) 99 to 80 mol% of ethylene, 1-butene 1 to 1 Ethylene / 1-butene copolymer with 20 mol%, preferably ethylene / 1-butene copolymer of 95-85 mol% ethylene and 5-15 mol% 1-butene, (4) ethylene 99-80 Ethylene / 1-octene copolymer of 1% by mole and 1 to 20% by mole of 1-octene, preferably 97 to 85% by mole of ethylene and 1% by mole of 1 to 1-octene Copolymers of an octene copolymer, (5) ethylene with up to 10 mol% of other alpha-olefins (except propylene, 1-butene, 1-octene) or vinyl monomers (for example, vinyl acetate, ethyl acrylate etc.) Ethylene copolymers such as polymers, (6) Propylene homopolymers, (7) Random copolymers of propylene and 30 mol% or less of other α-olefins, preferably propylene and 20 mol% or less Random copolymers with α-olefins, (8) block copolymers of propylene with up to 40 mol% of other α-olefins, (9) 1-butene homopolymer, (10) 1-butene and Random copolymer with 10 mol% or less of other α-olefin, (11) 4-Methyl-1-pentene homopolymer, (12) 4-methyl-1-pentene and 20 mol% or less Homopolymers and copolymers, such as with other α- olefin random copolymer and the like.

  Among these, (2) ethylene-propylene copolymer of 95 to 85 mol% of ethylene and 5 to 15 mol% of propylene, (3) 95 to 85 mol% of ethylene, and 5 to 15 mol% of 1-butene Ethylene / 1-butene copolymer, (4) ethylene / 1-octene copolymer of 97 to 85 mol% of ethylene and 3 to 15 mol% of 1-octene, (5) ethylene and 10 mol% Ethylene copolymers such as copolymers with the following other α-olefins (except for propylene, 1-butene and 1-octene) or vinyl monomers (for example, vinyl acetate, ethyl acrylate etc.), (6) propylene Homopolymers, (7) random copolymers of propylene and up to 20 mol% of other α-olefins, (8) block copolymers of propylene and up to 40 mol% of other α-olefins Homopolymers and copolymers of the body and the like are preferable.

[Laminate and method for producing the same]
The laminate of the present invention comprises an adhesive polymer composition in which at least a part thereof is in contact with the layer (A) on at least one side of a base layer (A) comprising a polymer (α) having an NH group at molecular terminals An adhesive layer (B) consisting of β) is laminated.

  The laminate of the present invention comprises an adhesive polymer composition in which at least a part thereof is in contact with the layer (A) on at least one side of a base layer (A) comprising a polymer (α) having an NH group at molecular terminals The polymer (α) and the polymer composition (β) are formed on the surface of the adhesive layer (B) on the side opposite to the side in contact with the layer (A). And a layer (C) composed of a polymer (γ) different from any of the above) is laminated on at least a part thereof.

In the laminate of the present invention, the layer (C) composed of the polymer (γ) is preferably composed of a polyolefin.
As a laminate according to the present invention, for example, a laminate of three types and three layers of (A) layer / (B) layer / (C) layer, and (A) layer / (B) layer / (C) layer Although a laminate of a three-kind five-layer structure of (B) layer / (A) layer or (C) layer / (B) layer / (A) layer / (B) layer / (C) layer is more preferable, It is not limited to.

The laminate of the present invention can be easily laminated and manufactured by a known molding method such as coextrusion molding method, lamination method, injection molding method and the like.
Although the manufacturing method of a laminated body is not specifically limited as long as the effect of this invention is produced, For example, the laminated body of the three-layer structure of (A) / (B) / (C) layer is manufactured by the following forming methods Can.

  The laminate is prepared by melting the polymer (α), the polymer composition for bonding (β) and the polymer (γ) in separate extruders, and then supplying them to a die having a three-layer structure to bond the polymer for bonding The composition (β) can be manufactured by coextrusion as an intermediate layer.

  In addition, the laminate previously forms a sheet of the base material layer (A) and the layer (C), and the adhesive polymer composition (β) is formed between the base material layer (A) and the layer (C). A method of melt extrusion (so-called sandwich laminating method) or a method of forming the base material layer (A), the adhesive layer (B) and the layer (C) in sheet form in advance and thermo-pressing these layers simultaneously (so-called It can also be manufactured by a known laminating method such as thermal laminating method). The heat laminating method includes a method of bonding using a heat press and a method of bonding continuously using a heat roll.

  Further, the laminate is produced by an injection molding method in which the polymer (α), the polymer composition for bonding (β) and the polymer (γ) are melted by separate extruders and then injected into a mold. It can also be done. In the injection molding method, a multicolor injection molding method in which a plurality of polymers are sequentially injected while changing the mold, or a preformed polymer is inserted into the mold and different polymers are inserted therein. The laminate can also be manufactured by insert molding for injection, or co-injection molding method for injecting into the same mold simultaneously or at different timings.

  The molding temperature is particularly limited as long as bonding is performed using a known molding method at the melting temperature of the adhesive polymer composition (β) (carbodiimide-modified polyolefin), preferably 180 ° C. or higher, more preferably 200 ° C. or higher. It may be different depending on various conditions such as the molding method, the molding process, and the type of raw material (polymer and composition). As a molding method, a coextrusion molding method, a lamination method or an injection molding method is preferable. When using these molding methods, the adhesive composition (β) can be obtained in consideration of the adhesion between the adhesive polymer composition (β) and the polymer (α), particularly the semiaromatic polyamide, and the physical properties of the entire laminate. The molding temperature is usually 180.degree. C. or higher, preferably a temperature above 180.degree. C., more preferably 200.degree. C. or higher, and the molding temperature of the polymer (.alpha.) Is fluid or various moldings at a temperature above its melting point. Although determined appropriately in consideration of the conditions, it is usually 320 ° C. or higher, preferably 330 ° C. or higher.

EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.
[Various measurement methods]
In the present example etc., measurement was carried out according to the following method.
[Melt flow rate (MFR)]
The measurement was carried out at 230 ° C. under a load of 2.16 kg according to ASTM D1238.
〔density〕
The density was measured in accordance with JIS K7112.
[Intrinsic viscosity [η]]
The intrinsic viscosity [η] of the polymer (α) was measured in a 96.5% sulfuric acid at a temperature of 25 ° C. using a Ubbelohde viscometer as a measuring device. Specifically, about 0.5 g of a polymer (α) having an NH group at the molecular end was dissolved in 50 ml of 96.5% concentrated sulfuric acid. The dropping second number of the obtained solution under the condition of 25 ± 0.05 ° C. was measured using a Ubbelode viscometer, and was calculated based on the following equation.
[Η] = ηSP / (C (1 + 0.205ηSP))
[Η]: Intrinsic viscosity (dl / g)
ηSP: specific viscosity C: sample concentration (g / dl)
The above ηSP was determined by the following equation.
ηSP = (t−t0) / t0
t: Seconds of flow of sample solution (seconds)
t0: Blank sulfuric acid flow down seconds (seconds)

[Melting point (Tm _A ) and glass transition temperature (Tg)]
The melting point (Tm) of the polymer (α) was measured using a differential scanning calorimeter (DSC 220C, manufactured by Seiko Instruments Inc.) as a measuring device. Specifically, about 5 mg of the polymer (α) was sealed in an aluminum pan for measurement and heated from room temperature to 340 ° C. at 10 ° C./min. In order to completely melt the polymer (α), it was held at 340 ° C. for 5 minutes, and then cooled to 30 ° C. at 10 ° C./min. After 5 minutes at 30 ° C., a second heating to 340 ° C. was performed at 10 ° C./min. The peak temperature (° C.) at this second heating was taken as the melting point (Tm) of the polymer (α), and the displacement point corresponding to the glass transition was taken as the glass transition temperature (Tg).

[Terminal NH ₂ Group Content of Polymer (α)]
The terminal amino group content [NH ₂ ] of the polymer (α) is measured by the following method. 0.5-0.7 g of semi-aromatic polyamide resin (A) is precisely weighed and dissolved in 30 mL of m-cresol. Then, 1 to 2 drops of a 0.1% thymol blue / m-cresol solution, which is an indicator, is added to prepare a sample solution. The terminal amino group content ([NH ₂ ], unit: μ equivalent / g) is specified by conducting titration of the sample solution with a 0.02 N p-toluenesulfonic acid solution from yellow to bluish purple Be done.

[Number average molecular weight of carbodiimide group-containing compound]
The number average molecular weight of the carbodiimide group-containing compound was measured at a column temperature of 40 ° C. using GPC (gel permeation chromatography) as a tetrahydrofuran solvent (mobile phase) (polystyrene conversion, Mw: weight average molecular weight, Mn: number average Molecular weight). For polystyrene having a molecular weight of 580 ≦ Mw ≦ 7 × 10 ⁶ , polystyrene PS-1 manufactured by Agilent Technology Co., Ltd. (formerly Polymer Laboratories Ltd.) was used.

[Content of carbodiimide group]
The carbodiimide group content was calculated from the preparation amount.

[Grafted amount of maleic anhydride]
The grafting amount of maleic anhydride was measured by the following method using FT-IR.
FT-IR measurement, 250 ° C. The sample heat Puresushi in 3 minutes - after making the bets, infrared spectrophotometer (JASCO Co., Ltd., FT-IR410 model) by a transmission method using 1790 cm ^- The infrared absorption spectrum around ¹ was measured. The measurement conditions were such that the resolution was 2 cm ^-1 and the number of integrations was 32.

[Reaction rate (%) of polyolefin (a) and carbodiimide group-containing compound (b)]
The reaction rate (%) was measured by FT-IR, and the grafted amount of maleic anhydride was measured to the adhesive polymer composition and the polyolefin (a) (maleic anhydride in the adhesive polymer composition) The light absorbency (1790 cm.sup.- ¹ ) derived from and the light absorbency derived from maleic anhydride in the polyolefin (a) were used to calculate by the above formula (2).

[Adhesive power of laminate]
The obtained laminate is cut into a width of 15 mm, and a semi-aromatic polyamide layer and a layer consisting of a polymer composition for adhesion (β) (CDI-PP1) by a 180 degree peel method using a tensile tester. Adhesive strength at the interface (unit: N / 15 mm) or at the interface between the semiaromatic polyamide layer and the layer consisting of MAH-PP (unit: N / 15 mm) at room temperature 23 ° C. and 100 ° C. It measured by. Further, the obtained laminate was subjected to retort treatment with warm water of 121 ° C. for 30 minutes, and the adhesion in a room temperature atmosphere was measured in the same manner as described above. The crosshead speed was 300 mm / min.

[Polyolefin used]
The polyolefins used in the examples and comparative examples are shown below. In addition, unless otherwise indicated, all commercially available products were used as this polyolefin.
(1) PP-1: polypropylene (random PP, MFR: 7 g / 10 min, density: 0.910 g / cm ³ , manufactured by Prime Polymer Co., Ltd.)
(2) MAH-PP-2: maleic anhydride modified polypropylene (MFR: 6 g / 10 min, density: 0.890 g / cm ³ , maleic anhydride grafting amount: 0.15%, manufactured by Mitsui Chemicals, Inc.)

Example 1
<Production of Polyolefin (a) Having a Group Reactive with a Carbodiimide Group>
1 part by weight of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as MAH) to 100 parts by weight of PP-1, 2,5-dimethyl-2,5-bis (tert-butylperoxy) A twin screw kneader (manufactured by Nippon Steel Co., Ltd., TEX-30, L / D) was mixed with 0.25 parts by weight of Hexin-3 (manufactured by NOF Corporation, trade name Perhexine (registered trademark) 25B). Using a vacuum vent: 40, extrusion was performed at a cylinder temperature of 220 ° C., a screw rotation speed of 200 rpm, and a discharge amount of 80 g / min to obtain a maleic acid-modified polypropylene (hereinafter abbreviated as MAH-PP-1). The density of MAH-PP-1 was 0.915 g / cm ³ .

  The resulting MAH-PP-1 was dissolved in xylene, and then the resulting xylene solution was poured into acetone to purify and reprecipitate MAH-PP-1. The graft amount of maleic anhydride was measured by FT-IR and found to be 0.7% by weight.

<Production of adhesive polymer composition (β)>
90 parts by weight of PP-1, 10 parts by weight of MAH-PP-1 prepared above, and a carbodiimide group-containing compound (manufactured by Nisshinbo Chemical Co., Ltd., trade name Carbodilight (registered trademark) HMV-8 CA, carbodiimide group equivalent 278, Number average molecular weight: 2100, 1.7 parts by weight of carbodiimide group number in one molecule: 9 parts are mixed, and a twin-screw kneader (manufactured by Japan Steel Works, TEX-30, L / D = 40, vacuum vent used) ) At a cylinder temperature of 250 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 80 g / min to produce an adhesive polymer composition (β) (hereinafter abbreviated as CDI-PP1).

The obtained CDI-PP1 had an MFR (230 ° C., 2.16 kg load) of 3 g / 10 min and a density of 0.910 g / cm ³ . According to FT-IR analysis, the peak (1790 cm ^-1 ) of maleic anhydride disappeared from CDI-PP1, so the absorbance derived from the group that reacts with the carbodiimide group of MAH-PP-1 The ratio of the difference (X) in absorbance derived from the group that reacts with the carbodiimide group in CDI-PP1 to the absorbance (Y) derived from the group that reacts with the carbodiimide group in MAH-PP-1 is 1 Therefore, the reaction rate of MAH-PP-1 and a carbodiimide group containing compound was 100%. The carbodiimide group content was 6.6 mmol (calculated from the preparation amount) per 100 g of the adhesive polymer composition (β).

<Preparation of Polymer (α) Having NH Group at Molecular End>
[1-1] Preparation of Semi-Aromatic Polyamide (α-1) (Polyamide 6T66) 2176 g (13.1 mol) of terephthalic acid, 2800 g (24.1 mol) of 1,6-hexanediamine, and 1578 g (10. 8 mol), 5.7 g of sodium hypophosphite monohydrate and 554 g of distilled water were charged in an autoclave of 13.6 L capacity and purged with nitrogen. Stirring was started from 190 ° C., and the internal temperature was raised to 250 ° C. over 3 hours. At this time, the internal pressure of the autoclave was raised to 3.01 MPa. The reaction was continued for 1 hour as it was, and then the reaction product was released to the atmosphere from a spray nozzle installed at the lower part of the autoclave to extract a low condensate. Thereafter, the low condensate was cooled to room temperature and pulverized by a pulverizer to a particle size of 1.5 mm or less. The ground product was then dried at 110 ° C. for 24 hours. The water content of the low condensate after drying was 3600 ppm, and the intrinsic viscosity [η] was 0.14 dl / g.

Next, this low condensate was placed in a tray type solid phase polymerization apparatus, and after nitrogen substitution, the temperature was raised to 220 ° C. over about 1 hour and 30 minutes. Thereafter, the low condensate was allowed to react for 1 hour, and was allowed to cool to room temperature. The intrinsic viscosity [η] of the obtained polyamide (high condensate) was 0.48 dl / g. Then, using a twin screw extruder with a screw diameter of 30 mm and L / D = 36, the polyamide (high condensate) is further melt polymerized at a barrel setting temperature of 330 ° C., a screw rotation speed of 200 rpm, and a polymer feed rate of 6 kg / h A semi-aromatic polyamide (α-1) was prepared. The limiting viscosity [η] of the obtained semiaromatic polyamide (α-1) was 1.0 dl / g, the melting point Tm _A was 310 ° C., the glass transition temperature was 85 ° C., and the terminal NH group content was 40 mmol / kg .

<Preparation of adhesive composition polymer composition (β) sheet>
The sheet | seat of the polymer composition ((beta)) for adhesion was created with the following method using an automatic press-forming machine (NSF50 made from Shinto Metal Industries, Ltd.).
Iron plate (3 mm) / aluminum plate (0.2 mm) / polyethylene fluoride sheet (0.3 mm) / gold frame (0.5 mm) / polyethylene fluoride sheet (0.3 mm) / aluminum plate (0.2 mm) / iron plate A pile was formed in the order of (3 mm), and a pellet of the polymer composition for adhesion (β) was spread inside the metal frame to make a molding unit. The molding unit is installed in an automatic press molding machine set to a heating temperature of 200 ° C., and heating is performed for 2 minutes without heating with a preheating time, and then heating for 2 minutes under a pressure of 40 kgf / cm ² Carried out.

Remove from the automatic press and transfer to another automatic press set at a temperature of 27 ° C, quench the forming unit under a pressure of 40 Kgf / cm ² for a cooling time of 2 minutes, sheet 0.5 mm thick Created. Moreover, the sheet | seat of 0.5 mm was created also about MAH-PP-2 by the same method as a comparative example.

<Preparation of semi-aromatic polyamide sheet>
Injection molding machine (Toshiba Machine Co., Ltd. EC75N-2A), molding machine cylinder temperature: 325 ° C., mold temperature: 2 mm of semi-aromatic polyamide (α-1) under molding conditions of 120 ° C. Square plate specimens were made.

<Preparation of polymer (γ) sheet>
Using the above-mentioned PP-1 as the polymer (γ), a sheet having a thickness of 0.5 mm was produced in the same manner as the production of the above-mentioned adhesive polymer composition (β) sheet.

<Creating a laminate>
The polymer composition for adhesion (β) sheet prepared above is overlapped with a semiaromatic polyamide sheet, and the semiaromatic polyamide side is formed using a heat sealing machine (TP-701-A · B manufactured by Tester Sangyo Co., Ltd.) The two-layer laminate for interlayer adhesion measurement was obtained by heat sealing at a temperature of 150 ° C., a temperature of 200 ° C. on the side of the adhesive polymer composition (β), a pressure of 0.1 MPa for 30 seconds.

  In addition, a polymer (γ) sheet, an adhesive polymer composition (β) sheet, and a semiaromatic polyamide sheet are laminated in this order and heat sealed under the same conditions to measure interlayer adhesion 3 A layer stack was obtained.

<Measurement of interlayer adhesion>
The interlayer adhesion of the laminate produced above was measured. The results are shown in Table 1.

Comparative Example 1
A laminate was obtained in the same manner as in Example 1 except that MAH-PP-2 was used as an adhesive layer in place of the adhesive polymer composition (β) used in Example 1.
The results are shown in Table 1.

[Discussion of the mechanism by which the water resistance is improved by the interaction between the terminal NH group of the polymer (α) and the carbodiimide-modified product of the composition (β)]
Although the reason for the difference in the adhesive strength in Example 1 and Comparative Example 1 described above is not clear, it is considered that the mechanism is as follows.
That is, when the maleic anhydride-modified polyolefin used in Comparative Example 1 is used as the adhesive polymer, covalent bonds or hydrogen bonds are formed with the terminal NH groups of the polyamide.

  On the other hand, when the CDI-PP1 [carbodiimide modified polyolefin] of Example 1 is used, the carbodiimide group contained in the carbodiimide modified polyolefin forms a covalent bond with the terminal NH group of the polyamide with high efficiency, and the hydrogen bond is not so much. It is guessed.

  Before retorting, both are considered to exhibit sufficient adhesion even at room temperature or 100 ° C. environment. However, hydrogen bonds are easily affected by water, so when retorted in warm water, the carbodiimide-modified polyolefin and the polyamide do not show a decrease in adhesion, whereas the maleic anhydride-modified polyolefin and the polyamide show remarkable adhesion. It is thought that the decline of

Claims (8)

Adhesive layer (B) comprising an adhesive polymer composition (β) satisfying the following (i) to (iii) on at least one side of a substrate layer (A) comprising a polymer (α) having an NH group at the molecular terminal A method of producing a laminate, comprising laminating
(I) A polyolefin formed by the reaction of a polyolefin (a) having a group reactive with a carbodiimide group and a carbodiimide group-containing compound (b) is included.
(Ii) It contains a carbodiimide group in an amount of 0.1 to 50 mmol per 100 g of the adhesive polymer composition.
(Iii) a density of ^{0.870g / cm 3 ~0.940g / cm 3} .   The polymer (α) and the polymer composition are provided on the side opposite to the side in contact with the layer (A) of the adhesive layer (B) of the adhesive layer (B) comprising the adhesive polymer composition (β) The method for producing a laminate according to claim 1, wherein a layer (C) comprising a polymer (γ) different from any of (β) is laminated on at least a part thereof.   The method for producing a laminate according to claim 1 or 2, wherein the polymer (α) having an NH group at the molecular terminal contains a semi-aromatic polyamide.   The method for producing a laminate according to claim 3, wherein the semiaromatic polyamide is composed of a dicarboxylic acid component unit (c1) and a diamine component unit (c2).   The method for producing a laminate according to claim 4, wherein the dicarboxylic acid component unit (c1) contains at least a terephthalic acid component unit.   The method for producing a laminate according to any one of claims 2 to 5, wherein the polymer (γ) contains a polyolefin.   After laminating the base material layer (A) and the adhesive layer (B) and optionally laminating the layer (C), the resulting laminate is retorted in warm water. The manufacturing method of the laminated body as described in any one of Claims 1-6. A base layer (A) comprising a polymer (α) having an NH group at a molecular end, and an adhesive layer (B) comprising an adhesive composition (β) at least a part of which is in contact with the layer (A) ,
A laminate, wherein the adhesive composition (β) satisfies the following (i) to (iii).
(I) A polyolefin formed by the reaction of a polyolefin (a) having a group reactive with a carbodiimide group and a carbodiimide group-containing compound (b) is included.
(Ii) It contains a carbodiimide group in an amount of 0.1 to 50 mmol per 100 g of the adhesive composition (β).
(Iii) a density of ^{0.870g / cm 3 ~0.940g / cm 3} .