JP2016190906A - Laminated body and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated body capable of enhancing a cohesive force and heat resistance of an adhesive composition, and to provide a method for producing the same.SOLUTION: A laminated body is a laminated body formed by laminating an adhesive layer on at least one surface of a foamed base material formed of a synthetic resin or rubber. The adhesive layer is formed of a photocurable adhesive composition that contains a monomer mixture (A) containing a (meth)acrylic ester monomer (a) having an alkyl group having 4 or more carbon atoms, a polymerizable monomer (b) having a nitrogen atom in a molecule and a predetermined (meth)acrylic ester monomer (c), a (meth)acrylic ester copolymer (B) which is copolymer of monomers containing the monomers (a), (b) and (c) in the monomer mixture (A), a predetermined isocyanate compound (C), a photopolymerization initiator (D), and a tackifying resin (F) which is a polymer of a polymerizable monomer containing a (meth)acrylic ester monomer.SELECTED DRAWING: None

Description

  The present invention relates to a laminate and a method for producing the same.

In a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer formed on a substrate (for example, see Patent Document 1), generally, a base polymer such as synthetic rubber has cohesion (holding power) and heat resistance. An isocyanate curing agent for improving the properties is added (see, for example, Patent Documents 2 to 4).
Here, as the isocyanate curing agent, (i) adduct type isocyanate, (ii) burette type isocyanate, (iii) isocyanurate type isocyanate, and the like are used.
The cohesive force and heat resistance of the pressure-sensitive adhesive composition are improved by the active hydrogen group (for example, hydroxyl group, carboxyl group, amino group, etc.) of the base polymer and the isocyanate group (NCO group) of the isocyanate curing agent. This is due to the increase in the crosslink density of the pressure-sensitive adhesive composition due to the reaction with (A).

JP 2005-82775 A JP 2002-241709 A JP 2001-49200 A JP 2011-46961 A

  In the laminated body which formed the adhesive composition on the base material by methods other than addition of the isocyanate hardening agent mentioned above, improving the cohesion force and heat resistance of an adhesive composition was desired. Moreover, it was calculated | required also about the improvement of the tackiness of an adhesive composition.

  Then, the objective of this invention is providing the laminated body which can improve the cohesion force and heat resistance of an adhesive composition, and its manufacturing method.

The laminate of the present invention is a laminate in which an adhesive layer is laminated on at least one surface of a foamed base material made of synthetic resin or rubber, and the adhesive layer is a monomer mixture (A). And a (meth) acrylic acid ester copolymer (B), a predetermined isocyanate compound (C), a photopolymerization initiator (D), and a tackifying resin (F). It is formed from an object.
According to this configuration, in the laminate, the isocyanate group in the predetermined isocyanate compound (C) is an active hydrogen group (for example, a hydroxyl group or a carboxyl group) present in the side chain of the (meth) acrylic acid ester copolymer (B). , Amino groups, etc.) and a crosslinked structure can be formed to improve the cohesive force and heat resistance of the photocurable pressure-sensitive adhesive composition. The improvement of the anchoring property is manifested when the predetermined isocyanate compound (C) forms a crosslinked structure with the (meth) acrylic acid ester copolymer (B) and the tackiness is improved. Moreover, since the said tackifying resin (F) is a polymer of the polymerizable monomer containing a (meth) acrylic acid ester monomer, the adhesiveness is maintained while maintaining the compatibility of the contained components. Can be improved. Furthermore, the anchoring property of the photocurable pressure-sensitive adhesive composition can be further improved by using a foamed base material made of synthetic resin or rubber as the adherend.

  Here, when the foamed substrate is made of at least one selected from the group consisting of urethane foam and ethylene / propylene / diene rubber (EPDM) foam, the anchoring property of the photocurable pressure-sensitive adhesive composition is further improved. Can be made.

  Here, the content of the isocyanate compound (C) is 100 in total of the monomer compound (A), the (meth) acrylic acid ester copolymer (B), and the photopolymerization initiator (D). When it is 1 part by mass to 5 parts by mass with respect to part by mass, the anchoring property and curved surface followability of the photocurable adhesive composition are improved while further improving the cohesive force and heat resistance of the photocurable adhesive composition. Can be further improved.

  Further, here, when the polymerizable monomer (b) having a nitrogen atom in the molecule in the monomer mixture (A) is at least one of N-vinylpyrrolidone and dimethylaminoethyl methacrylate, it is obtained. It is preferable in terms of easiness, polymerizability, and characteristics of the (meth) acrylic acid ester copolymer (B) to be obtained.

  The (meth) acrylic acid ester copolymer (B) has a weight average molecular weight (Mw) of 200,000 to 400,000, and a ratio (Mw) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). / Mn) when the dispersity is 2.0 to 5.0 and the side chain has 3 to 10 mol of polymerizable double bond per mol of copolymer molecule, holding power, tackiness (initial adhesion) The adhesive performance such as property) and curability can be maintained, and it is possible to prevent the viscosity from increasing and the coating from becoming difficult.

  Moreover, here, the polymerizable double bond of the side chain of the (meth) acrylic acid ester copolymer (B) is glycidyl acrylate or glycidyl methacrylate, and the monomer in the monomer mixture (A). When it is introduced by reacting with a copolymer of monomers containing (a), (b) and (c), it is preferable in terms of availability, cost and the like.

  Moreover, here, when the said photocurable adhesive composition further contains chlorinated polypropylene (E), it can express favorable adhesiveness to the polypropylene base material with which adhesion is usually difficult.

  Moreover, here, when the weight average molecular weight (Mw) of the tackifying resin (F) is more than 20,000 and not more than 150,000, the adhesiveness is further improved while reliably maintaining the compatibility of the components. be able to.

  Moreover, here, when the said tackifier resin (F) is a polymer which does not have a polymerizable double bond, it can prevent that hardening inhibition arises.

Here, when the photocurable pressure-sensitive adhesive composition is curable with ultraviolet rays having an irradiation intensity of 10 to 1,000 mW / cm ² and an integrated light amount of 10 to 1,000 mJ / cm ² , the ultraviolet rays are used under the specific conditions. By irradiating and curing, the anchoring property of the photocurable pressure-sensitive adhesive composition can be further improved.

The manufacturing method of the laminated body of this invention manufactures the laminated body of this invention, Comprising: Irradiation intensity | strength 10-1,000 mW / cm < ² >, integrated light quantity 10-1, 1 is manufactured to the said photocurable adhesive composition. It includes an ultraviolet irradiation step of irradiating ultraviolet rays of 000 mJ / cm ² .
According to this structure, the anchoring property of a photocurable adhesive composition can be improved more.

  In the present specification, (i) “(meth) acrylic acid” means acrylic acid and / or methacrylic acid, (ii) “(meth) acrylate” means acrylate and / or methacrylate, (Iii) “monomer mixture” means a mixture of a plurality of types of monomers; (iv) “copolymer” means a polymer in which a plurality of types of monomers are copolymerized; (V) “Polymerizable double bond” means a double bond that contributes to polymerization such as a carbon-carbon double bond, and (vi) “weight average molecular weight (Mw)” of isocyanate compound (C) is isocyanate. It means a value calculated based on NCO% (measured by JIS K1603-1B method) in compound (C). (Vii) “Number average molecular weight (Mn)” of isocyanate compound (C) is isocyanate compound (C) In The value calculated based on NCO% (measured by JIS K1603-1B method), (viii) “mol number of polymer” is obtained by dividing the weight of the obtained polymer by the weight average molecular weight. (Ix) “mol number of polymerizable double bond” means the number of moles of the reacted compound, and (x) “isocyanate group was removed from the diisocyanate compound having two NCO groups in the molecule. “Residue” means, for example, a carbon bond part (hydrocarbon) having 1 to 80 carbon atoms, and (xi) “residue obtained by removing a hydroxyl group from a diol compound having two OH groups in the molecule” is For example, it means a carbon bond part (hydrocarbon) having 1 to 80 carbon atoms.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body which can improve the cohesion force and heat resistance of an adhesive composition can be provided.

FIG. 1 is a schematic diagram for explaining a method for evaluating a cohesive force (holding force). FIG. 2 is a schematic diagram for explaining a method for producing an evaluation sample used for evaluating the cohesive force (holding force). FIG. 3 is a schematic diagram for explaining an evaluation method of heat resistance (high temperature side softening point). FIG. 4 is a schematic diagram for explaining an evaluation method of water resistance (hot water peeling test).

  Below, the form for implementing this invention is illustrated.

(Laminate)
The laminate of the present invention is formed by laminating an adhesive layer on at least one surface of a foamed substrate.
As the laminate of the present invention, for example, (i) a base material 240 (corresponding to a foamed base material in the present invention) as shown in FIG. 2, an adhesive layer 230 formed on the base material 240, and an adhesive (Ii) a base material 310 (corresponding to a foam base material in the present invention) as shown in FIG. 3, and a base material 310 formed on the base material 310. A laminate comprising an adhesive layer 350, a core material 320 formed on the adhesive layer 350, an adhesive layer 330 formed on the core material 320, and a release paper 340 formed on the adhesive layer 330. Body, etc.

<Foamed substrate>
The material of the foam base material as the adherend is not particularly limited as long as it is made of synthetic resin or rubber, and can be appropriately selected according to the purpose.
Hereinafter, “synthetic resin” and “rubber” will be described.

<< Synthetic resin >>
The synthetic resin is not particularly limited as long as it is a foamed synthetic resin, and can be appropriately selected according to the purpose. For example, a foamed urethane resin (urethane foam), a foamed polyethylene resin (polyethylene foam), polystyrene, polyolefin , Etc. These may be used individually by 1 type and may use 2 or more types together.
Among these, a foamed urethane resin (urethane foam) such as a high-density foamed urethane resin or a medium-density foamed urethane resin is preferable in terms of providing a laminate with the pressure-sensitive adhesive composition.

<< Rubber >>
The rubber is not particularly limited as long as it is foamed rubber, and can be appropriately selected according to the purpose. For example, ethylene / propylene / diene rubber (EPDM) such as Everlite Moran 830 (manufactured by Bridgestone Corporation) is used. Examples thereof include foamed rubber (EPDM foam) as a main component. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as thickness of the said foaming base material, Although it can select suitably according to the objective, 3-30 mm is preferable.

<Photocurable adhesive composition>
The photocurable pressure-sensitive adhesive composition in the present invention comprises at least a monomer mixture (A), a (meth) acrylic acid ester copolymer (B), an isocyanate compound (C), and a photopolymerization initiator (D ) And a tackifier resin (F), and further, if necessary, other components.

（式中、Ｒ^１は水素原子又はメチル基、ｎは０〜６の整数を表し、複数のｎが混在してもよい。） << monomer mixture (A) >>
The monomer mixture (A) constitutes a base polymer together with the (meth) acrylic acid ester copolymer (B) described later, and is a (meth) acrylic acid ester having at least an alkyl group having 4 or more carbon atoms. A monomer (a), a polymerizable monomer (b) having a nitrogen atom in the molecule, and a (meth) acrylate monomer (c) represented by the following general formula (1) And further contains other monomers as necessary.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, n represents an integer of 0 to 6, and a plurality of n may be mixed.)

-(Meth) acrylate monomer (a)-
The (meth) acrylic acid ester monomer (a) is not particularly limited as long as it has an alkyl group having 4 or more carbon atoms, and can be appropriately selected according to the purpose. For example, n-butyl acrylate, Isobutyl acrylate, tertiary butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, n-butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, cyclohexyl methacrylate, methacrylic acid 2-ethylhexyl, lauryl methacrylate, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, n-butyl acrylate and 2-ethylhexyl acrylate are preferable in terms of availability, polymerizability, and characteristics of the obtained polymer.
There is no restriction | limiting in particular as content of the said (meth) acrylic acid ester monomer (a), Although it can select suitably according to the objective, 60 mass with respect to the said monomer mixture (A). % To 95% by mass is preferable, 70% to 95% by mass is more preferable, and 80% to 95% by mass is particularly preferable. When the content of the (meth) acrylic acid ester monomer (a) is less than 60% by mass, the glass transition temperature of the photocurable pressure-sensitive adhesive composition is increased, and the adhesiveness to the foamed substrate is reduced. If it exceeds 95% by mass, the cohesive force of the photocurable pressure-sensitive adhesive composition may be insufficient, and the adhesive performance such as holding power may be reduced.

-Polymerizable monomer (b)-
The polymerizable monomer (b) is not particularly limited as long as it has a nitrogen atom in the molecule, and can be appropriately selected according to the purpose. For example, dimethylaminoethyl methacrylate (N, N-methacrylate) Dimethylaminoethyl, etc.), N, N-diethylaminoethyl methacrylate, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine , 3-methacryloyloxyethylethylene urea, N-vinylpyrrolidone (N-vinyl-2-pyrrolidone, etc.), N-vinylcaprolactam, acrylonitrile, acryloylmorpholine, methacryloylmorpholine, acrylamide, N, N-dimethylacrylamide, ethylacrylamide, isopropyl Acrylamide N-methylolacrylamide, 2-hydroxyethylacrylamide, N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide, methacrylamide, N, N-dimethylmethacrylamide, ethylmethacrylamide, isopropylmethacrylamide, N-methylol Examples include methacrylamide, 2-hydroxyethyl methacrylamide, N, N-dimethylaminopropyl methacrylamide, N, N-diethylaminopropyl methacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, at least one of N-vinylpyrrolidone (N-vinyl-2-pyrrolidone, etc.) and dimethylaminoethyl methacrylate (N, N-dimethylaminoethyl methacrylate, etc.) is easily available, polymerizable, It is preferable at points, such as the characteristic of the (meth) acrylic acid ester copolymer (B) obtained.
There is no restriction | limiting in particular as content of the said polymerizable monomer (b), Although it can select suitably according to the objective, 3 mass%-30 mass with respect to the said monomer mixture (A). % Is preferable, 5% by mass to 25% by mass is more preferable, and 5% by mass to 20% by mass is particularly preferable. When the content of the polymerizable monomer (b) is less than 3% by mass, the cohesive force may be insufficient, and adhesive performance such as holding power may be reduced. The transition temperature rises and the adhesion to the foamed substrate may be reduced.

（式中、Ｒ^１は水素原子又はメチル基、ｎは０〜６の整数を表し、複数のｎが混在してもよい。）
入手し易さの点では、アクリル酸、メタクリル酸、が好ましく、また、その後の変性の反応性の点では、２−カルボキシエチルアクリレートオリゴマーが好ましい。
前記（メタ）アクリル酸エステル単量体（ｃ）の含有量としては、特に制限はなく、目的に応じて適宜選択することができるが、前記単量体混合物（Ａ）に対して、１質量％〜３０質量％が好ましく、３質量％〜２５質量％がより好ましく、５質量％〜２０質量％が特に好ましい。前記（メタ）アクリル酸エステル単量体（ｃ）の含有量が、１質量％未満であると、凝集力が不足し、保持力等の粘着性能が減じられることがあり、３０質量％超であると、ガラス転移温度が上昇し、発泡基材への粘着性が減じられることがある。 -(Meth) acrylate monomer (c)-
The (meth) acrylic acid ester monomer (c) is not particularly limited as long as it is represented by the following general formula (1), and can be appropriately selected according to the purpose. For example, acrylic acid, methacrylic acid , 2-carboxyethyl acrylate oligomer, and the like. These may be used individually by 1 type and may use 2 or more types together. Note that acrylic acid and methacrylic acid (that is, (meth) acrylic acid (when n = 0 in the following general formula)) are also included in the (meth) acrylic acid ester monomer (c).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, n represents an integer of 0 to 6, and a plurality of n may be mixed.)
Acrylic acid and methacrylic acid are preferable in terms of availability, and a 2-carboxyethyl acrylate oligomer is preferable in terms of the reactivity of subsequent modification.
There is no restriction | limiting in particular as content of the said (meth) acrylic acid ester monomer (c), Although it can select suitably according to the objective, 1 mass with respect to the said monomer mixture (A). % To 30% by mass is preferable, 3% to 25% by mass is more preferable, and 5% to 20% by mass is particularly preferable. When the content of the (meth) acrylic acid ester monomer (c) is less than 1% by mass, the cohesive force may be insufficient, and the adhesive performance such as holding power may be reduced. In some cases, the glass transition temperature increases and the adhesion to the foamed substrate may be reduced.

-Other monomers-
The other monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-methacrylic acid 2- Hydroxyl-containing monomers such as hydroxyethyl, hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate; Derived from dicyclopentadiene such as pentanyloxyethyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate That the acrylic monomers; allyl acrylate, allyl methacrylate, benzyl methacrylate, such as tetrahydrofurfuryl methacrylate (meth) acrylic acid ester monomer; and the like. These may be used individually by 1 type and may use 2 or more types together.

<< (Meth) acrylic acid ester copolymer (B) >>
The (meth) acrylic acid ester copolymer (B) constitutes a base polymer together with the monomer mixture (A), and the monomers (a), ( It is a copolymer of monomers containing b) and (c). That is, the (meth) acrylic acid ester copolymer (B) includes at least a (meth) acrylic acid ester monomer (a), a polymerizable monomer (b), and a (meth) acrylic acid ester monomer. When it is a copolymer with the monomer (c) and there is any other monomer, it may or may not be contained in the copolymer component.
The weight average molecular weight (Mw) of the (meth) acrylic acid ester copolymer (B) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 200,000 to 400,000. 200,000-350,000 is more preferable, and 200,000-300,000 is particularly preferable.
When the weight average molecular weight (Mw) of the (meth) acrylic acid ester copolymer (B) is less than 200,000, cohesive force may be insufficient, and adhesive performance such as holding power may be reduced. 400 If it exceeds 1,000, the viscosity increases and coating may be difficult.
The degree of dispersion (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the (meth) acrylic acid ester copolymer (B) is not particularly limited and may be appropriately selected depending on the intended purpose. 2.0 to 5.0, 2.0 to 4.0 are more preferable, and 2.0 to 3.5 are particularly preferable.
When the degree of dispersion (Mw / Mn) of the (meth) acrylic acid ester copolymer (B) is less than 2.0, initial tackiness (initial tackiness) may be reduced, and more than 5.0 If it is, the cohesive force is insufficient, and the adhesive performance such as holding force may be reduced.

The (meth) acrylic acid ester copolymer (B) preferably has a polymerizable double bond in the copolymer side chain. In this case, the copolymer part can also be imparted with polymerization reactivity at the time of curing, and can be cured with less energy during the curing reaction, and the adhesion performance is further improved by increasing the cohesive force by increasing the molecular weight. It is also possible to do.
The modification method for introducing a polymerizable double bond into the copolymer side chain is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it has a functional group such as a hydroxyl group, an epoxy group, or a carboxyl group. After copolymerization of the monomers (after obtaining a copolymer of the monomers including the monomers (a), (b) and (c) in the monomer mixture (A)), these functionalities Examples thereof include a method of introducing a compound having a functional group capable of reacting with a group and a polymerizable double bond into a copolymer side chain by addition reaction. Here, the carboxyl group introduced into the side chain of the copolymer by copolymerizing the (meth) acrylic acid ester monomer (c) represented by the general formula (1) described above reacts with the carboxyl group. It is preferred to add the compound. The compound that reacts with the carboxyl group is not particularly limited and may be appropriately selected depending on the purpose.Glycidyl acrylate or glycidyl methacrylate having an epoxy group is easy to obtain and costs. preferable.
The number of moles of the polymerizable double bond in the copolymer side chain is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 3 mol to 10 mol per mol of the copolymer (B) molecule, 4 mol to 10 mol are more preferable, and 5 mol to 10 mol are particularly preferable. If the number of moles of the polymerizable double bond in the copolymer side chain is less than 3 mol, sufficient curability may not be obtained when cured, and if it exceeds 10 mol, Adhesive performance may be reduced.
The (meth) acrylic acid ester copolymer (B) has a weight average molecular weight (Mw) of 200,000 to 400,000, and a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). It is preferable that the dispersity represented by (Mw / Mn) is 2.0 to 5.0, and the side chain has 3 to 10 mol of polymerizable double bonds per mol of the copolymer molecule.

-Manufacturing method of (meth) acrylic acid ester copolymer (B)-
There is no restriction | limiting in particular as a manufacturing method of the said (meth) acrylic acid ester copolymer (B), The weight average molecular weight (Mw) and dispersion degree (Mw /) of the said (meth) acrylic acid ester copolymer (B). Mn) and the amount of the polymerizable double bond in the side chain can be appropriately selected, but the mixture of the monomer mixture (A) and the (meth) acrylate copolymer (B) is safe. In addition, bulk polymerization using living radical polymerization is preferable in that it can be easily obtained. Specifically, a (meth) acrylic acid ester monomer (a) having an alkyl group having 4 or more carbon atoms, a polymerizable monomer (b) having a nitrogen atom in the molecule, and the general formula (1) A mixture X containing the (meth) acrylic acid ester monomer (c) represented is prepared (preparation step), and preferably 20% by mass to 60% by mass of the total amount of the prepared mixture X. Preferably, 30% by mass to 55% by mass, and more preferably 30% by mass to 50% by mass is mass-polymerized (converted) using living radical polymerization to form a (meth) acrylic acid ester copolymer (B). (Polymerization step), a mixture of the monomer mixture (A) and the (meth) acrylic acid ester copolymer (B) can be obtained. When the ratio of converting the mixture X to a polymer is less than 20% by mass, the adhesion and curing functions of the polymer part may not be sufficiently exhibited, and when it exceeds 60% by mass, the monomer In some cases, the viscosity of the mixture of the mixture (A) and the (meth) acrylic acid ester copolymer (B) increases, making coating difficult.

Further, in the method for producing the (meth) acrylic acid ester copolymer (B), for the purpose of controlling heat generation, which is difficult with ordinary bulk polymerization, bulk polymerization using a living radical whose reaction rate can be controlled (living) It is preferable to apply radical bulk polymerization).
There is no restriction | limiting in particular as said living radical polymerization, According to the objective, it can select suitably, For example, unstable radical polymerization, atom transfer polymerization, addition open type chain transfer polymerization, etc. are mentioned.
Among these, addition open-chain type chain transfer polymerization is preferable from the viewpoint of easy availability and cost of the catalyst to be used.
In living radical bulk polymerization to obtain a mixture of the monomer mixture (A) and the (meth) acrylic acid ester copolymer (B), the addition open chain transfer agent (d) has a 10-hour half-life temperature. Manufactured by a method in which 2 mol times or more of the polymerization initiator (e) at 30 ° C. to 50 ° C. is used and the first polymerization reaction is carried out at 50 ° C. or less and then the second polymerization reaction is carried out at 60 ° C. to 100 ° C. It is preferable to do. Thereby, the (meth) acrylic acid ester copolymer (B) whose molecular weight and dispersion degree satisfy | fill the said range can be obtained efficiently.

The addition open-chain transfer agent (d) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, α-methylstyrene dimer, 2-cyano-2-propylbenzodithionate, cyanomethyl Dodecyl trithiocarbonate, bis (thiobenzoyl) disulfide, and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, α-methylstyrene dimer represented by the following structural formula, that is, 2,4-diphenyl-4-methyl-1-pentene, is preferable because it is easily available and inexpensive.

前記重合開始剤（ｅ）の１０時間半減期温度としては、特に制限はなく、目的に応じて適宜選択することができるが、３０℃〜５０℃が好ましく、３０℃〜４５℃がより好ましく、３０℃〜４０℃がさらに好ましく、３０℃〜３５℃が特に好ましい。
前記重合開始剤（ｅ）の１０時間半減期温度が３０℃未満であると、前記重合開始剤（ｅ）の投入直後に一時的に大きな発熱が起こることがあり、前記重合開始剤（ｅ）の１０時間半減期温度が５０℃超であると、前記重合開始剤（ｅ）の投入直後の急な発熱は抑制できるが反応が進行しない場合や、反応時間が長い場合や、またその後重合温度を高くした際に一時的に大きな発熱が起こる場合があるため安全な塊状重合ができないことがある。ここで、前記１０時間半減期温度は、重合開始剤濃度が１０時間で半減する温度を指し、重合開始剤の生産メーカーが公表している値を採用した。

The 10-hour half-life temperature of the polymerization initiator (e) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 30 ° C to 50 ° C, more preferably 30 ° C to 45 ° C, 30 to 40 degreeC is further more preferable, and 30 to 35 degreeC is especially preferable.
If the 10-hour half-life temperature of the polymerization initiator (e) is less than 30 ° C., a large exotherm may occur temporarily immediately after the polymerization initiator (e) is added, and the polymerization initiator (e) When the 10-hour half-life temperature is more than 50 ° C., sudden exotherm immediately after the polymerization initiator (e) is charged can be suppressed, but the reaction does not proceed, the reaction time is long, or the polymerization temperature is increased thereafter. When the temperature is increased, a large exotherm may occur temporarily, so that safe bulk polymerization may not be possible. Here, the 10-hour half-life temperature refers to a temperature at which the polymerization initiator concentration is reduced to half in 10 hours, and a value published by the manufacturer of the polymerization initiator was adopted.

The polymerization initiator (e) having a 10-hour half-life temperature of 30 ° C. to 50 ° C. is not particularly limited and can be appropriately selected according to the purpose. 2′-Azobis (4-methoxy-2,4-dimethylvaleronitrile) (“V-70” manufactured by Wako Pure Chemical Industries, Ltd.) (10 hour half-life temperature 30 ° C.), diisobutyl peroxide (manufactured by NOF Corporation “Perloyl”) IB ”) (10-hour half-life temperature 33 ° C.), cumyl peroxyneodecanate (“ PARK MIL ND ”manufactured by NOF Corporation) (10-hour half-life temperature 37 ° C.), dinormalpropyl peroxydicarbonate (NOF Corporation) “Perloyl NPP” (10 hours half-life temperature 40 ° C.), diisopropyl peroxydicarbonate (“Paroyl IPP” manufactured by NOF Corporation) (10 hours half-life temperature 41 ° C.), disecondary Butyl peroxydicarbonate (Nippon "Perloyl SBP") (10 hour half-life temperature 41 ° C), 1,1,3,3-tetramethylbutyl peroxyneodecanoate (Nippon "Perocta ND" ”) (10-hour half-life temperature 41 ° C.), di (4-tert-butylcyclohexyl) peroxydicarbonate (“ PAROIL TCP ”manufactured by NOF Corporation) (10-hour half-life temperature 41 ° C.), 1-cyclo Hexyl-1-methylethyl peroxyneodecaate (“Nippon Co., Ltd.“ Percyclo ND ”) (10-hour half-life temperature 41 ° C.), di (2-ethoxyethyl) peroxydicarbonate (manufactured by NOF Corporation“ Parroyl EEP ") (10-hour half-life temperature 43 ° C), di (2-ethylhexyl) peroxydicarbonate (" PAROIL OPP "manufactured by NOF Corporation) (10-hour half-life temperature) 44 ° C.), Tertiary hexyl peroxyneodecaate (“NOF Corporation“ Perhexyl ND ”) (10 hour half-life temperature 45 ° C.), Dimethoxybutyl peroxydicarbonate (NOF Corporation“ Perroyl NBP ”) (10 Time half-life temperature 46 ° C.), tertiary butyl peroxyneodecanoate (“Perbutyl ND” manufactured by NOF Corporation) (10-hour half-life temperature 46 ° C.), and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (“V-70” manufactured by Wako Pure Chemical Industries, Ltd.) (10-hour half-life temperature 30 ° C.), diisobutyl peroxide ( NOF "PAROIL IB" (10-hour half-life temperature 33 ° C), cumyl peroxyneodecate (NOF "PARK MIL ND") (10-hour half-life temperature 37 ° C) has a polymerization temperature control. It is preferable because it is easy, the polymerization rate is high, and the production time can be shortened.

There is no restriction | limiting in particular as the addition amount of the said addition open-chain type chain transfer agent (d), Although it can select suitably according to the objective, The said polymerization initiator whose 10-hour half-life temperature is 30 degreeC-50 degreeC 2 mol times or more is preferable with respect to the addition amount of (e), 2 mol times-50 mol times are more preferable, 2 mol times-35 mol times are further more preferable, 2 mol times-20 mol times are especially preferable.
When the addition amount of the additional open chain transfer agent (d) is 2 mol times or more with respect to the addition amount of the polymerization initiator (e) whose 10-hour half-life temperature is 30 ° C. to 50 ° C. The speed is controlled appropriately, the amount of heat generated during production is easily controlled, the acrylate copolymer can be produced safely, and safe bulk polymerization is possible.
On the other hand, the addition amount of the additional open-chain transfer agent (d) is less than 2 mol times the addition amount of the polymerization initiator (e) whose 10-hour half-life temperature is 30 ° C. to 50 ° C. When the acrylate copolymer is produced from the acrylate monomer, rapid and intense heat generation may occur, leading to a runaway reaction.

There is no restriction | limiting in particular as reaction temperature in a said 1st polymerization reaction, Although it can select suitably according to the objective, 50 degrees C or less is preferable and 25 to 50 degreeC is more preferable.
There is no restriction | limiting in particular as reaction temperature in said 2nd polymerization reaction, Although it can select suitably according to the objective, 60 to 100 degreeC is preferable, 60 to 90 degreeC is more preferable, and 60 to 80 degreeC. ° C is particularly preferred.

  By carrying out the polymerization at a preferable temperature as described above, a polymerization intermediate is obtained by the first polymerization reaction, and then the living polymerization is carried out by the second polymerization reaction, whereby a copolymer having a plurality of peaks is obtained. As a result, not only the desired molecular weight (Mw) but also the degree of dispersion (Mw / Mn) that tends to be small in normal living polymerization can be efficiently obtained in the range of 2.0 to 5.0.

<< Total content of monomer mixture (A) and (meth) acrylic acid ester copolymer (B) >>
The total content of the monomer mixture (A) and the (meth) acrylic acid ester copolymer (B) is not particularly limited and may be appropriately selected depending on the intended purpose. 80 mass%-99.3 mass% is preferable with respect to the whole agent composition, 85 mass%-95 mass% is more preferable, 90 mass%-95 mass% is especially preferable. When the total content is less than 80% by mass, the effects of curability and pressure-sensitive adhesive properties may be reduced, and when it exceeds 99.3% by mass, the effects of curability and pressure-sensitive physical properties are obtained. The effects of the monomer mixture (A) and other components may not be sufficiently exhibited.

<< Isocyanate compound (C) >>
The isocyanate compound (C) in the present invention is a compound represented by the following general formula (2), and the compound is a bifunctional prepolymer type isocyanate curing agent having isocyanate (NCO) groups at both ends. .
(Chemical formula 2)
^{NCO-R 2 -NHCOO-P-} NHCOO-R 3 -OCN (2)
(In the formula, R ² represents a residue obtained by removing an isocyanate group from a diisocyanate compound having two NCO groups in the molecule, and R ³ is a residue obtained by removing the isocyanate group from a diisocyanate compound having two NCO groups in the molecule. Represents a group, and P represents a residue obtained by removing an OH group from a diol compound having two OH groups in the molecule.)
By using the isocyanate compound (C), an active hydrogen group (for example, hydroxyl group, carboxyl group, amino group) present in the side chain of the (meth) acrylate copolymer (B) in the photocurable pressure-sensitive adhesive composition. Group) and a crosslinked structure can be formed to improve the cohesive force of the photocurable pressure-sensitive adhesive.

There is no restriction | limiting in particular as content of the said isocyanate compound (C), Although it can select suitably according to the objective, The said monomer compound (A), the said (meth) acrylic acid ester copolymer (B ) And a total of 100 parts by mass of the photopolymerization initiator (D), preferably 1 part by mass to 5 parts by mass, and more preferably 3 parts by mass to 5 parts by mass.
When the content of the isocyanate compound (C) is less than 1 part by mass, the cohesive force of the photocurable pressure-sensitive adhesive composition is not improved, and the adhesive performance (holding force) may be reduced. If it is super, the transferability of the photocurable pressure-sensitive adhesive composition to the foamed substrate may be lowered. On the other hand, when it is within the more preferable range, it is advantageous in that the deterioration of the adhesive performance (holding force) of the photocurable adhesive composition and the transferability to the foamed substrate can be further prevented.

There is no restriction | limiting in particular as a weight average molecular weight (Mw) of the said isocyanate compound (C), Although it can select suitably according to the objective, 200-1,300 are preferable and 400-1,300 are more preferable.
If the weight average molecular weight (Mw) of the isocyanate compound (C) is less than 200, the cohesive force at high temperatures may be reduced. On the other hand, when the weight average molecular weight (Mw) of the isocyanate compound (C) is within the more preferable range, it is advantageous in that the characteristics are more manifested.
The weight average molecular weight (Mw) is calculated from the following calculation formula.
Weight average molecular weight (Mw) = 4200 / NCO%
Here, NCO% is measured by the JIS K1603-1B method.

The isocyanate compound (C) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI).
There is no restriction | limiting in particular as a specific example of the commercial item of the said tolylene diisocyanate (TDI), According to the objective, it can select suitably, For example, Death module E-14 (made by Sumika Bayer Urethane Co., Ltd.), Death Module E-15 (manufactured by Sumika Bayer Urethane Co., Ltd.) and the like can be mentioned.
There is no restriction | limiting in particular as a specific example of the commercial item of the said diphenylmethane diisocyanate (MDI), According to the objective, it can select suitably, For example, Sumidur E-21 (made by Sumika Bayer Urethane Co., Ltd.), SBU isocyanate 0620 (manufactured by Sumika Bayer Urethane Co., Ltd.), Death Module E-23 (manufactured by Sumika Bayer Urethane Co., Ltd.), and the like.

  When using the said isocyanate compound (C), it is preferable that it is a thing which does not contain a solvent substantially.

<< Photoinitiator (D) >>
The photopolymerization initiator (D) has a function of absorbing radicals such as ultraviolet rays. By containing this photopolymerization initiator (D), the curing reaction can be initiated by irradiation with light such as ultraviolet rays.
There is no restriction | limiting in particular as said photoinitiator (D), According to the objective (The wavelength of the ultraviolet-ray irradiated at the time of hardening, a cured film thickness, etc.), it can select suitably, For example, a benzophenone, 2,2'- Dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-hydroxy-1- ( 4- (4- (2-hydroxy-2-methyl-propionyl) -benzyl) phenyl) -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- (4- ( Methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1- ON, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, bis (2,4,6-trimethylbenzoyl) phenylphos Examples include fin oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, benzophenone, 2,2′-dimethoxy-1,2-diphenylethane-1-one, and 1-hydroxy-cyclohexyl-phenyl-ketone are preferable in terms of availability and cost. (2,4,6-Trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are preferred in terms of thick film curing.

  There is no restriction | limiting in particular as content of the said photoinitiator (D), Although it can select suitably according to the objective, 0.2 mass%-10 mass% with respect to the whole photocurable adhesive composition. % By mass is preferable, 0.5% by mass to 8% by mass is more preferable, and 1% by mass to 6% by mass is particularly preferable. When the content of the photopolymerization initiator (D) is less than 0.2% by mass, the curing rate is lowered, and the odor may be deteriorated by the remaining unreacted monomer. When it exists, solubility may worsen and a turbidity, a buzz, and yellowing may generate | occur | produce in a molded article.

  There is no restriction | limiting in particular as a mixing method of the said photoinitiator (D), Although it can select suitably according to the objective, It is preferable to melt | dissolve and mix in a monomer in consideration of solubility. After mixing, a curing reaction occurs due to ultraviolet rays, and light shielding is required. Therefore, the monomer mixture (A), the (meth) acrylic acid ester copolymer (B), and the tackifier resin (C It is preferable that the mixture is finally mixed into the mixture.

  In addition, when using the said photoinitiator (D), it is preferable that it is a thing which does not contain a solvent substantially.

<< Tackifier Resin (F) >>
The tackifier resin (F) is a polymer of a polymerizable monomer containing a (meth) acrylic acid ester monomer. Here, the tackifier resin (F) is a polymer that does not have a polymerizable double bond in terms of prevention of curing inhibition (a polymer that does not have a double bond capable of terminating a polymerization chain). It is preferable that In addition, when a photocurable adhesive composition contains tackifying resin (F) here, the adhesiveness to a foaming base material can be improved, and a softening point falls and heat resistance falls. Can be prevented.

  There is no restriction | limiting in particular as a weight average molecular weight (Mw) of the said tackifying resin (F), Although it can select suitably according to the objective, More than 20,000 and 150,000 or less are preferable, 30,000- 137,000 is more preferable, 37,000 to 137,000 is particularly preferable, and 37,000 to 60,000 is most preferable. When the weight average molecular weight (Mw) of the tackifying resin (F) is 20,000 or less, the tackiness may be lowered, and when it is more than 150,000, the compatibility of the components may be lowered. is there. On the other hand, when the molecular weight of the tackifying resin (F) is within a more preferable range, particularly preferable range, or most preferable range, the molecular weight of the tackifying resin (F) is an appropriate value. By passing too much, the entanglement between the (meth) acrylic acid ester copolymer (B) and the tackifier resin (F) is easily unraveled, and it is reliably prevented that the adhesive property is deteriorated, and When the molecular weight of the tackifying resin (F) is too large, the (meth) acrylic acid ester copolymer (B) and the tackifying resin (F) are less likely to be entangled, resulting in a decrease in the adhesive properties. This is advantageous in that it can be reliably prevented.

  There is no restriction | limiting in particular as content of the said tackifying resin (F), Although it can select suitably according to the objective, The said monomer mixture (A) and the said (meth) acrylic acid ester copolymer 0.5 parts by weight to 40 parts by weight is preferable, 1 part by weight to 9 parts by weight is more preferable, and 2.8 parts by weight with respect to (B) and a total of 100 parts by weight of the photopolymerization initiator (D). ˜4.8 parts by mass is particularly preferred. When the content of the tackifying resin (F) is less than 0.5 parts by mass, the adhesion performance (throwing property) and transferability with the foamed substrate may be reduced, and the content is more than 40 parts by mass. And the compatibility of a component may fall. On the other hand, when the content of the tackifying resin (F) is in a more preferable range or in a particularly preferable range, the effect of the tackifying resin (F) can be expressed more highly. It is advantageous.

  The glass transition temperature of the tackifying resin (F) is not particularly limited and may be appropriately selected depending on the intended purpose. However, the glass transition temperature of the photocurable pressure-sensitive adhesive composition is controlled within a target temperature range. And 40 degreeC or more is preferable at the point which can control the tackiness etc. which express in a predetermined temperature range, and 40 to 180 degreeC is more preferable.

-(Meth) acrylate monomer-
There is no restriction | limiting in particular as (meth) acrylic acid ester monomer for comprising the said tackifying resin (F), According to the objective, it can select suitably, For example, (meth) acrylic acid and carbon (Meth) acrylic acid alkyl ester with an alcohol having an alkyl group of 1 to 20, preferably 1 to 4, an ester of (meth) acrylic acid with an alicyclic alcohol having 3 to 14 carbon atoms, (meth) acrylic Examples thereof include esters of an acid and an aromatic alcohol having 6 to 14 carbon atoms. These may be used individually by 1 type and may use 2 or more types together.
Among these, (i) (meth) acrylic acid and (meth) acrylic acid alkyl ester of (meth) acrylic acid and an alcohol having an alkyl group having 1 to 4 carbon atoms and / or (ii) (meth) acrylic acid and 3 to 14 carbon atoms. And (iii) an ester of (meth) acrylic acid and benzyl alcohol (a kind of aromatic alcohol having 6 to 14 carbon atoms).

Specific examples of the (meth) acrylate monomer include methyl (meth) acrylate (for example, methyl methacrylate), ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate ( For example, tert-butyl methacrylate), pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylate-2-ethylhexyl, octyl (meth) acrylate, nonyl (meth) acrylate, (meth) acryl (Meth) acrylic acid alkyl esters such as decyl acid and dodecyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl acrylate, isobornyl methacrylate, tricyclodecanyl acrylate, tricyclodecanyl methacrylate, etc. (Meth) acrylic acid and alicyclic alcohol Esters of Le; (meth) acrylate, phenyl (meth) (meth) acrylic acid aryl esters of benzyl acrylate and the like; and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, cyclohexyl methacrylate, isobornyl acrylate, methyl methacrylate, tert-butyl methacrylate, tricyclodecanyl acrylate, tricyclodecanyl methacrylate, and isobornyl methacrylate are the glass transition of the photocurable pressure-sensitive adhesive composition. When controlling temperature to the target temperature range, it is possible by addition of a small amount, and it is preferable at the point which can improve the adhesive characteristic at high temperature.

  The tackifier resin (F) can be prepared using the (meth) acrylic acid ester monomer as a main component as a monomer having a polymerizable unsaturated bond. Accordingly, the tackifying resin (F) is preferably a repeating unit derived from the (meth) acrylic acid ester monomer as described above ((meth) acrylic acid ester component unit) in terms of monomer. Is 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more.

The tackifying resin (F) has a repeating unit derived from a monomer copolymerizable with a (meth) acrylic acid ester monomer in addition to the above (meth) acrylic acid ester component unit. It may be.
There is no restriction | limiting in particular as a monomer copolymerizable with the said (meth) acrylic acid ester monomer, According to the objective, it can select suitably, For example, (meth) acrylic acid, (meth) acrylic acid Alkoxyalkyl (meth) acrylates such as methoxyethyl, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate; alkali (meth) acrylate Salts such as metal salts; di (meth) acrylic acid ester of ethylene glycol, di (meth) acrylic acid ester of diethylene glycol, di (meth) acrylic acid ester of triethylene glycol, di (meth) acrylic acid ester of polyethylene glycol, Di (meth) acrylic acid ester of propylene glycol, zip Di (meth) acrylic acid ester of pyrene glycol, di (meth) acrylic acid ester of tripropylene glycol, etc. Di (meth) acrylic acid ester of (poly) alkylene glycol; trimethylolpropane tri (meth) acrylic acid ester, etc. Polyvalent (meth) acrylic acid ester; (meth) acrylonitrile; vinyl acetate; vinylidene chloride; halogenated vinyl compounds such as (meth) acrylic acid-2-chloroethyl; 2-vinyl-2-oxazoline, 2-vinyl-5 Oxazoline group-containing polymerizable compounds such as methyl-2-oxazoline and 2-isopropenyl-2-oxazoline; Aziridine group-containing polymerizable compounds such as (meth) acryloylaziridine and (meth) acrylic acid-2-aziridinylethyl; Allyl glycidyl ether, (meth) acrylic Epoxy group-containing vinyl monomers such as acid glycidyl ether, (meth) acrylic acid glycidyl ether, (meth) acrylic acid-2-ethylglycidyl ether; (meth) acrylic acid-2-hydroxyethyl, acrylic acid-2- Hydroxypropyl, monoesters of (meth) acrylic acid and polypropylene glycol or polyethylene glycol, hydroxyl group-containing vinyl compounds such as adducts of lactones and (meth) acrylic acid-2-hydroxyethyl; fluorine-substituted methacrylic acid alkyl esters , Fluorine-containing vinyl monomers such as fluorine-substituted acrylic acid alkyl esters; unsaturated carboxylic acids such as itaconic acid, crotonic acid, maleic acid and fumaric acid (excluding (meth) acrylic acid), salts thereof and these (Partial) ester compound and acid anhydride Reactive halogen-containing vinyl monomers such as 2-chloroethyl vinyl ether and vinyl monochloroacetate; Amide-containing vinyl such as methacrylamide, N-methylol methacrylamide, N-methoxyethyl methacrylamide, N-butoxymethyl methacrylamide Monomer; Organosilicon group-containing vinyl compound monomer such as vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, allyltrimethoxysilane, trimethoxysilylpropylallylamine, 2-methoxyethoxytrimethoxysilane; Examples include macromonomers having a radical polymerizable vinyl group at the terminal of a monomer obtained by polymerizing a vinyl group (for example, fluorine-based monomer, silicon-containing monomer, macromonomer, styrene, silicon, etc.). These may be used individually by 1 type and may use 2 or more types together.

In the tackifying resin (F), the introduction of a functional group having reactivity with an isocyanate group makes it easier to react with the isocyanate compound (C), or the cohesive force can be improved. In terms, it is preferable.
Specific examples of the functional group include a hydroxyl group, a carboxyl group, an amino group, an amide group, a mercapto group, and the like.
In producing the tackifying resin (F), it is preferable to use a monomer having the functional group. The tackifying resin (F) is different from the (meth) acrylic acid ester copolymer (B).
Moreover, it is preferable that the monomer which forms the said tackifying resin (F) differs from the monomer in the said monomer mixture (A). The tackifying resin (F) and the monomers ((meth) acrylic acid ester monomer (a), (meth) acrylic acid ester monomer (c)) in the monomer mixture (A); Has a common unit called (meth) acrylic acid ester, the tackifier resin (F) is a monomer ((meth) acrylic acid ester monomer in the monomer mixture (A). It dissolves well in (a) and (meth) acrylic acid ester monomer (c)).

  Specific examples of the tackifying resin (F) include polycyclohexyl methacrylate, polytricyclodecanyl methacrylate, polyisobornyl methacrylate, a copolymer of isobutyl methacrylate and methacrylic acid, and the like.

<< Other ingredients >>
The photocurable pressure-sensitive adhesive composition of the present invention is chlorinated polypropylene (E); calcium carbonate, aluminum hydroxide, silica, clay, talc, titanium oxide, etc., as necessary, without departing from the spirit of the present invention. Inorganic materials such as glass balloons, shirasu balloons and ceramic balloons; organic materials such as nylon beads, acrylic beads and silicon beads; organic hollow materials such as vinylidene chloride balloons and acrylic balloons; foaming agents; dyes; pigments; Agents; stabilizers; and the like.

-Chlorinated polypropylene (E)-
By containing the chlorinated polypropylene (E), the photocurable pressure-sensitive adhesive composition of the present invention can exhibit good adhesiveness to a polypropylene substrate that is usually difficult to stick.
There is no restriction | limiting in particular as said chlorinated polypropylene (E), According to the objective, it can select suitably, For example, what is marketed, such as HARDREN (made by Toyobo), Sparklon (made by Nippon Paper Chemicals), etc. , Etc. These may be used individually by 1 type and may use 2 or more types together.
Among these, the pellet type thing which is not diluted with the solvent is preferable at the point which is a material which does not contain a solvent.
There is no restriction | limiting in particular as said hard ren series, According to the objective, it can select suitably, For example, 13-LP, 13-LLP, 14LWP, 15-LLP, 16-LP, DX-523P, DX-526P , DX-530P, and the like. These may be used individually by 1 type and may use 2 or more types together. Since these differences are different in molecular weight and degree of chlorination, a grade of chlorination degree suitable for solubility and compatibility can be arbitrarily selected.
Among these, DX-523P, DX-526P, and DX-530P are preferable in terms of solubility and compatibility.

  There is no restriction | limiting in particular as content of the said chlorinated polypropylene (E), Although it can select suitably according to the objective, 0.5 mass%-10 mass with respect to the whole photocurable adhesive composition. % Is preferable, 1% by mass to 8% by mass is more preferable, and 2% by mass to 6% by mass is particularly preferable. When the content of the chlorinated polypropylene (E) is less than 0.5% by mass, the improvement in adhesiveness to the polypropylene substrate may be insufficient, and when the content is more than 10% by mass, the photocurable adhesive is used. The viscosity of the composition may increase, making coating difficult.

  There is no restriction | limiting in particular as a mixing method of the said chlorinated polypropylene (E), Although it can select suitably according to the objective, It considers solubility and it is preferable to melt | dissolve and mix in a monomer. Here, it may be dissolved in the monomer mixture (A) before bulk polymerization, or may be mixed in a mixture of the monomer mixture (A) and the (meth) acrylic ester copolymer (B). .

<Curing characteristics of photocurable pressure-sensitive adhesive composition>
The curing characteristics of the photocurable pressure-sensitive adhesive composition will be described.
The photocurable pressure-sensitive adhesive composition can be cured with ultraviolet rays having an irradiation intensity of 10 to 1,000 mW / cm ² and an integrated light amount of 10 to 1,000 mJ / cm ² .

-Irradiation intensity-
The irradiation intensity is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably ^{10~1,000mW / cm 2, 50~100mW / cm} 2 is more preferable.
-Integrated light intensity-
As integrated light quantity is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10~1,000mJ / cm ^2, more preferably 20-250mJ / cm ^2, is 90-150mJ / cm ² Even more preferred. In addition, when both irradiation intensity and integrated light quantity are in the said preferable range, the anchoring property of a photocurable adhesive composition can be improved more, and bonding without crimping | compression-bonding will be attained.

(Manufacturing method of laminate)
The manufacturing method of the laminated body of this invention includes an ultraviolet irradiation process at least, and also includes an application | coating process, a drying process, and another process as needed.
The method for producing a laminate of the present invention can be used effectively in order to obtain the above-described laminate of the present invention, and is performed, for example, in the order of a coating process, a drying process, and an ultraviolet irradiation process.

<Ultraviolet irradiation process>
The ultraviolet irradiation step is a step of irradiating the photocurable pressure-sensitive adhesive composition with ultraviolet rays having a predetermined irradiation intensity so as to have a predetermined integrated light amount.
-Irradiation intensity-
There is no restriction | limiting in particular as long as it is 10-1,000 mW / cm < ² > as irradiation intensity, Although it can select suitably according to the objective, 50-100 mW / cm < ² > is preferable.
-Integrated light intensity-
The integrated light amount is not particularly limited as long as it is 10 to 1,000 mJ / cm ² , and can be appropriately selected according to the purpose, but is preferably 100 to 200 mJ / cm ² .
In addition, when both irradiation intensity and integrated light quantity are in the said preferable range, the anchoring property of a photocurable adhesive composition can be improved more, and bonding without crimping | compression-bonding will be attained.

<Application process>
An application process is a process of apply | coating a photocurable adhesive composition to the at least one surface of a foaming base material.
The application method is not particularly limited and can be appropriately selected according to the purpose (application amount, shape of the application surface). Examples of the application method include a bar coater method, a roll coater method, a curtain flow method, Spray method, etc.

<Drying process>
A drying process is a process of drying the foaming base material with which the photocurable adhesive composition was apply | coated to at least one surface.
There is no restriction | limiting in particular as drying temperature, According to the objective, it can select suitably.
There is no restriction | limiting in particular as drying time, According to the objective, it can select suitably.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

<Measurement method of analytical values and characteristics>
The analytical values and characteristics shown in Tables 1 and 2 were measured by the following method.

-Weight average molecular weight (Mw) and number average molecular weight (Mn) ((meth) acrylic acid ester copolymer (B), isocyanate compound (C), tackifying resin (F))-
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated based on the NCO% (measured by the JIS K1603-1B method) in the isocyanate compound (C).
The dispersity (Mw / Mn) was determined by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn). Table 1 shows the weight average molecular weight (Mw) and dispersity (Mw / Mn) of the (meth) acrylic acid ester copolymer (B).
The number average molecular weight (Mn) and the weight average molecular weight (Mw) are calculated from the following calculation formulas.
Weight average molecular weight (Mw) = 4200 / NCO%
Here, NCO% is measured by JIS K1603-1 B method.

-Polymerization state (mainly exothermic state) ((meth) acrylic acid ester copolymer (B))-
The exothermic state when polymerizing the (meth) acrylic acid ester copolymer (B) was determined according to the following criteria. The results are shown in Table 1.
○ (Pass): No sudden exotherm was observed and the set temperature ± 2 ° C. could be maintained in all reaction steps. × (Fail): Exotherm exceeding 3 ° C. in 10 seconds, or all reaction steps When the set temperature ± 2 ° C could not be maintained due to heat generation or endotherm.

-Polymer conversion (unit: mass%) (monomer mixture (A) and (meth) acrylic acid ester copolymer (B) mixture)-
The heating residue (mass%) was measured according to JIS K5407: 1997, and this was defined as the polymer conversion rate (mass%). However, the heating conditions were a temperature of 140 ° C. and a time of 30 minutes.
The results are shown in Table 1.

-Reaction rate of glycidyl (meth) acrylate (unit: mass%) ((meth) acrylic acid ester copolymer (B))-
Using high-performance liquid chromatography (HPLC) (Shimadzu test equipment), distilled water and acetonitrile as eluents, using a reverse-phase column and an ultraviolet detector, the internal standard method (standard material anisole) was used to remain (meta ) Glycidyl acrylate was quantified. Using this value, the reaction rate of glycidyl (meth) acrylate was calculated from the following formula.

−重合体（ポリマー）１ｍｏｌあたりの二重結合ｍｏｌ数（単位：ｍｏｌ）（（メタ）アクリル酸エステル共重合体（Ｂ））−
次式によって算出した。結果を表１に示す。

-Number of moles of double bond per mol of polymer (polymer) (unit: mol) ((meth) acrylic acid ester copolymer (B))-
It was calculated by the following formula. The results are shown in Table 1.

−ガラス転移温度（Ｔｇ）（粘着付与性樹脂（Ｆ））−
粘着付与性樹脂（Ｆ）のガラス転移温度を、粘弾性測定装置（セイコーインスツルメンツ製）を用いて測定した。

-Glass transition temperature (Tg) (tackifying resin (F))-
The glass transition temperature of the tackifier resin (F) was measured using a viscoelasticity measuring device (manufactured by Seiko Instruments).

-Cohesive strength (holding power) (photo-curable adhesive composition)-
As shown in FIG. 1, the sample produced by the production method shown in FIG. 2 below is cut into 25 mm × 50 mm. Next, half (25 mm × 25 mm) of the cut evaluation sample 600 is bonded to a 50 mm × 300 mm PP plate 610 as an adherend with an adhesive 620. Next, a 5 kg roller is reciprocated once on the bonded portion (25 mm × 25 mm) and left at room temperature for 24 hours. Next, the evaluation sample 600 was sandwiched between jigs 630 (100 g), and a 1 kg load (weight) 640 was suspended from the jig 630. Next, by taking the time from when the load (weight) 640 is suspended (A in FIG. 1) to dropping (B in FIG. 1) as a measured value, the photocurable adhesive is compliant with JISZ0237. The cohesive strength (holding power) of the composition was evaluated. The evaluation criteria are as follows. The results are shown in Table 2. The test environment was a temperature of 23 ° C. and a humidity of 50%.
-Evaluation sample preparation method-
As shown in FIG. 2, the area of 100 mm × 150 mm and the film thickness of 60 μm ± 5 μm are formed on the release paper 200 by using a variable bar coater for the photocurable adhesive composition of each composition (Table 2). To form a pressure-sensitive adhesive layer (uncured) 210 (coated with a pressure-sensitive adhesive), and then irradiate from the pressure-sensitive adhesive layer (uncured) 210 side in an irradiation environment under a nitrogen atmosphere (oxygen concentration of 1,000 ppm). UV220 was applied so that the intensity and integrated light amount were as shown in Table 3 (UV irradiation), and the adhesive layer was cured to form an adhesive layer (cured) 230. Then, various (Table 2) base materials 240 having a thickness of 10 mm are bonded to the pressure-sensitive adhesive layer (curing) 230 side (base material bonding). The evaluation sample 100 was produced by rotating and crimping (crimping), and leaving it at room temperature for 24 hours after the crimping.
-Evaluation criteria-
◎: More than 60 minutes ○: More than 20 minutes and less than 60 minutes △: More than 5 minutes and less than 20 minutes ×: Less than 5 minutes-: Evaluation not possible

-Heat resistance (softening point on the high temperature side) (photo-curable adhesive composition)-
As shown in FIG. 3, the produced sample is cut into 25 mm × 50 mm in the same manner as the evaluation sample used in the evaluation of cohesive force (holding force) (as shown in FIG. 2). Next, half of the cut evaluation sample 700 (25 mm × 25 mm) is bonded to a 50 mm × 100 mm PP plate 710 as an adherend with an adhesive 720. Next, a 5 kg roller is reciprocated once on the bonded portion (25 mm × 25 mm) and left at room temperature for 24 hours. Next, the evaluation sample 700 was sandwiched between jigs 730 (100 g), and a load (weight) 740 of 500 g was suspended from the jig 730. Next, by measuring the time from suspending the load (weight) 740 (A in FIG. 3) to dropping (B in FIG. 3) as a measurement value, a 3D BANK SHEAR TESTER manufactured by Chemistments is used. The heat resistance of the curable adhesive composition was evaluated. The evaluation criteria are as follows. The results are shown in Table 2. The test environment was a temperature of 23 ° C to 110 ° C.
-Evaluation criteria-
A: Over 70 ° C. ○: Over 55 ° C. and under 70 ° C. Δ: Over 40 ° C. and under 55 ° C. x: Less than 40 ° C. −: Not applicable

-Water resistance (photo-curable adhesive composition)-
As shown in FIG. 4, the produced sample is cut into 25 mm × 350 mm in the same manner as the evaluation sample used in the evaluation of the cohesive force (holding force) (as shown in FIG. 2). Next, a 25 mm × 150 mm region of the cut evaluation sample 800 is bonded to a 50 mm × 300 mm PP plate 810 as an adherend with an adhesive 820. Next, a 2 kg roller is reciprocated once on the bonded portion (25 mm × 150 mm) and left at room temperature for 24 hours. Next, the evaluation sample 800 bonded to the PP plate 810 is immersed in hot water at 80 ° C. for 72 hours. Cool the hot water to room temperature. Next, the PP plate 810 was attached to the chuck 830, and the undried evaluation sample 800 was attached to the chuck 840 (A in FIG. 4). Next, various base materials / adhesive interfaces were peeled off at 300 mm / min, and from the point where the peeling behavior was stabilized, the integral average value up to 100 mm was taken as the measured value, and STA-1150 manufactured by ORIENTEC was used. A peel test was performed to evaluate the water resistance of the photocurable pressure-sensitive adhesive composition. The evaluation criteria are as follows. The results are shown in Table 2.
-Evaluation criteria-
☆: More than 5N / 25mm ◎: More than 4N / 25mm 5N / 25mm or less ○: More than 3N / 25mm 4N / 25mm or less △: 1N / 25mm more than 3N / 25mm or less X: Less than 1N / 25mm-: Not evaluated

<Preparation of monomer mixture (A) and (meth) acrylic acid ester copolymer (B) mixture>
A “monomer mixture (A) and (meth) acrylic acid ester copolymer (B) mixture” having the composition and physical properties shown in Table 1 were prepared as follows.

Synthesis Example 1
2-Lethylhexyl acrylate ((meth) acrylic acid ester monomer having an alkyl group having 4 or more carbon atoms (a) is added to a 2 L four-necked flask having a nitrogen gas inlet tube, a reflux condenser, a stirring device, and a charging port. 830 g, N-vinylpyrrolidone (polymerizable monomer having a nitrogen atom in the molecule (b)) 120 g, acrylic acid ((meth) acrylic acid ester monomer represented by the general formula (1) (c )) 50 g and 1 g of α-methylstyrene dimer (chain transfer agent (d)) (6.5 mol times the polymerization initiator) were added and stirred while bubbling with nitrogen gas to adjust the temperature of the mixture to 50 ° C. Next, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (“V-70” manufactured by Wako Pure Chemical Industries, Ltd., 10 hour half-life temperature 30 ° C.) (polymerization initiator (e)) 0.2 g was added. After reacting for 2 hours while keeping the temperature at 50 ° C., the temperature is raised to 70 ° C., and when the polymer conversion rate becomes about 45 mass%, the supply air in the flask is switched from nitrogen to air. 0.5 g of p-methoxyphenol was added to stop the reaction. Next, 3 g of glycidyl methacrylate (polymerizable group introducing agent) and 4 g of N, N′-dimethylbenzylamine were added and reacted at 90 ° C. for 6 hours while bubbling with air to obtain monomer mixtures (A) and ( A mixture P-1 of a (meth) acrylic acid ester copolymer (B) was prepared.
The obtained mixture P-1 was able to be produced without any problem in safety because no rapid exotherm was observed within the entire reaction time. The other evaluation results are shown in Table 1.

-Synthesis Example 2-
Using the same apparatus as in Synthesis Example 1, 250 g of 2-ethylhexyl acrylate ((meth) acrylate monomer (a) having an alkyl group having 4 or more carbon atoms), n-butyl acrylate (carbon number) 550 g of (meth) acrylic acid ester monomer (a) having 4 or more alkyl groups, 150 g of acrylamide (polymerizable monomer (b) having a nitrogen atom in the molecule), β-CEA (Rhodia Nikka) Manufactured) ((meth) acrylic acid ester monomer (c) represented by the general formula (1)) 50 g, α-methylstyrene dimer (chain transfer agent (d)) 1 g (6.5 mol of polymerization initiator) The mixture was stirred while bubbling with nitrogen gas, and the temperature of the mixture was adjusted to 50 ° C. Next, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (“V-70” manufactured by Wako Pure Chemical Industries, Ltd., 10 hour half-life temperature 30 ° C.) (polymerization initiator (e)) 0.2 g was added. After reacting for 2 hours while maintaining the temperature at 50 ° C., the temperature was raised to 70 ° C., and when the polymer conversion rate was about 45% by mass, the reaction was stopped in the same manner as in Synthesis Example 1. . Next, 2.5 g of glycidyl methacrylate (polymerizable group introducing agent) was reacted to prepare a mixture P-2 of the monomer mixture (A) and the (meth) acrylic ester copolymer (B).
The obtained mixture P-2 was able to be produced without any safety problem because no rapid exotherm was observed within the entire reaction time. The other evaluation results are shown in Table 1.

Synthesis Example 3-
Using the same apparatus as in Synthesis Example 1, 440 g of 2-ethylhexyl acrylate ((meth) acrylate monomer (a) having an alkyl group having 4 or more carbon atoms), n-butyl acrylate (carbon number) 400 g of (meth) acrylic acid ester monomer (a) having 4 or more alkyl groups, 100 g of methyl methacrylate (other monomers), dimethylaminoethyl methacrylate (polymerizable monomer having a nitrogen atom in the molecule) 30 g of monomer (b), 30 g of methacrylic acid ((meth) acrylic acid ester monomer (c) represented by the general formula (1)), 10 g of α-methylstyrene dimer (chain transfer agent (d)) (13.0 mol times the polymerization initiator) was charged and stirred while bubbling with nitrogen gas, and the temperature of the mixture was adjusted to 25 ° C. Next, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (“V-70” manufactured by Wako Pure Chemical Industries, Ltd., 10 hour half-life temperature 30 ° C.) (polymerization initiator (e)) 1 g was added and reacted while raising the temperature to 50 ° C. over 2.5 hours, then the temperature was raised to 85 ° C., and when the polymer conversion rate became 55% by mass, Synthesis Example 1 The reaction was stopped as described above. Next, 4.5 g of glycidyl methacrylate was reacted to prepare a mixture P-3 of the monomer mixture (A) and the (meth) acrylic acid ester copolymer (B).
The obtained mixture P-3 was able to be produced without any problem in safety because no rapid exotherm was observed within the entire reaction time. The other evaluation results are shown in Table 1.

Synthesis Example 4-
In Synthesis Example 1, a mixture P-4 was obtained in the same manner as in Synthesis Example 1 except that 3 g of glycidyl methacrylate was changed to 3 g of glycidyl acrylate.
The obtained mixture P-4 was able to be produced without any problem in safety because no rapid exotherm was observed within the entire reaction time. The other evaluation results are shown in Table 1.

-Synthesis Comparative Example 1
In Synthesis Example 3, the charged composition was 920 g of methyl methacrylate (other monomer), 30 g of dimethylaminoethyl methacrylate (polymerizable monomer (b) having a nitrogen atom in the molecule), acrylic acid (general Prepared in the same manner as in Synthesis Example 3 except that it was changed to 50 g of the (meth) acrylic acid ester monomer (c) represented by the formula (1), and the polymer conversion rate was about 50% by mass. The reaction was stopped at. Next, 2.5 g of glycidyl methacrylate was reacted to prepare a mixture P-5 of the monomer mixture (A) and the (meth) acrylic acid ester copolymer (B).
The obtained mixture P-5 was able to be produced without any problem in safety because no rapid exotherm was observed within the entire reaction time. The other evaluation results are shown in Table 1.

-Synthetic Comparative Example 2-
In Synthesis Example 1, the charged composition was 950 g of 2-ethylhexyl acrylate ((meth) acrylate monomer (a) having an alkyl group having 4 or more carbon atoms), acrylic acid (represented by the general formula (1)). The (meth) acrylic acid ester monomer (c)) was prepared in the same manner as in Synthesis Example 1 except that the amount was changed to 50 g, and the reaction was stopped when the polymer conversion rate was about 45% by mass. . Next, 2.5 g of glycidyl methacrylate was reacted to prepare a mixture P-6 of the monomer mixture (A) and the (meth) acrylic acid ester copolymer (B).
The obtained mixture P-6 was able to be produced without any problem in safety because no rapid exotherm was observed within the entire reaction time. The other evaluation results are shown in Table 1.

-Synthetic Comparative Example 3-
In Synthesis Example 1, the charged composition was 880 g of 2-ethylhexyl acrylate ((meth) acrylate monomer (a) having an alkyl group having 4 or more carbon atoms), N-vinylpyrrolidone (nitrogen atom in the molecule) The polymerizable monomer (b)) was prepared in the same manner as in Synthesis Example 1 except that the polymerizable monomer (b) was changed to 120 g, and the reaction was stopped when the polymer conversion rate was about 45% by mass. Next, 2.5 g of glycidyl methacrylate was reacted to prepare a mixture P-7 of the monomer mixture (A) and the (meth) acrylic acid ester copolymer (B).
The obtained mixture P-7 was able to be produced without any problem in safety because no rapid exotherm was observed within the entire reaction time. The other evaluation results are shown in Table 1.

<Preparation of tackifying resin (F)>
A tackifying resin was prepared by further polymerization using a partially polymerized syrup prepared as described below so that the polymerization rate was 100%.
-Preparation of partially polymerized syrup-
Cyclohexyl methacrylate monomer (Tg: 66 ° C.) is charged as a polymerizable monomer into a 2 liter four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and cooling tube, and the molecular weight As a regulator, 0.2 g of n-dodecyl mercaptan (NDM) was added, and the temperature was raised to 60 ° C. under a nitrogen stream to stop heating.

  Next, 0.2 g of azobisisobutyronitrile as a polymerization initiator was added with stirring, and the reaction was performed for 30 minutes to obtain a partially polymerized syrup TF. The weight average molecular weight was 17,000.

  Each component was mix | blended with the prescription shown in Table 2 (The value in each component represents a mass part), and the photocurable adhesive composition was prepared. And it measured and evaluated about the cohesion force (holding force), heat resistance, and water resistance by the method mentioned above. The results are shown in Table 2. In addition, Table 3 shows the coating conditions and irradiation conditions in the evaluation.

In Table 2, the materials used are as follows.
(I) Mixtures / mixtures P-1 to P-7 of monomer mixture (A) and (meth) acrylic acid ester copolymer (B): Synthesis Examples 1 to 4 and Synthesis Comparative Examples 1 to 3 described above (Ii) Isocyanate Compound (C)
E-14: Desmodur E-14 (manufactured by Sumika Bayer Urethane Co., Ltd .: prepolymer tolylene diisocyanate (TDI) (aromatic isocyanate) represented by the above formula (2), weight average molecular weight (Mw) : 1100-1300)
(Iii) Photopolymerization initiator (D)
・ Lucirin TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by BASF Japan (iv) Chlorinated polypropylene (E)
DX-530P: Toyobo Co., Ltd. chlorinated polypropylene (v) tackifying resin (F)
-Tackifying resin TF: obtained by the above-described preparation method (vi) Urethane foam 1 (base material): polyether-based polyurethane foam (density: 18.0 to 22.0 kg / m ³ , hardness: 95 N -135N, Elongation: 130% or more, Tensile strength: 70 kPa or more, Compression residual strain: 6.0% or less)
(Vii) Urethane foam 2 (base material): polyether-based polyurethane foam (density: 47.0 to 55.0 kg / m ³ , hardness: 0.20 kg / cm ^{2 to} 0.50 kg / cm ² , elongation: (50% or more, tensile strength: 17.7 kPa or more, compressive residual strain: 20.0% or less)
(Viii) EPDM foam (base material): semi-closed cell foam mainly composed of EPDM synthetic rubber (density: 80 to 120 kg / m ³ , elongation: 200% or more, tensile strength: 39 kPa or more, warm compression Residual strain: 40% or less)

From Table 2, the pressure-sensitive adhesive layer is laminated on at least one surface of the foamed base material made of synthetic resin or rubber, and the pressure-sensitive adhesive layer contains the following (A) to (D) and (F). It turns out that the laminated body of Examples 1-10 formed from the curable adhesive composition can improve the cohesive force and heat resistance of an adhesive composition, and is excellent.
(A): a (meth) acrylic acid ester monomer (a) having an alkyl group having 4 or more carbon atoms, a polymerizable monomer (b) having a nitrogen atom in the molecule, and the general formula (1) A monomer mixture (A) comprising a (meth) acrylic acid ester monomer (c) represented by:
(B): (meth) acrylic acid ester copolymer (B) which is a copolymer of monomers including the monomers (a), (b) and (c) in the monomer mixture (A). );
(C): Isocyanate compound (C) represented by the above general formula (2);
(D): Photopolymerization initiator (D);
(F): Tackifying resin (F) which is a polymer of a polymerizable monomer containing a (meth) acrylic acid ester monomer.

200 Release paper 210 Adhesive layer (uncured)
220 UV
230 Adhesive layer (cured)
240 Substrate 600 Evaluation Sample 610 PP Plate 620 Adhesive 630 Jig 640 Load (Weight)
700 Evaluation Sample 710 PP Plate 720 Adhesive 730 Jig 740 Load (Weight)
800 Evaluation Sample 810 PP Plate 820 Adhesive 830 Chuck 840 Chuck

Claims (11)

A laminate in which an adhesive layer is laminated on at least one surface of a foamed base material made of synthetic resin or rubber,
The pressure-sensitive adhesive layer is
A (meth) acrylic acid ester monomer (a) having an alkyl group having 4 or more carbon atoms, a polymerizable monomer (b) having a nitrogen atom in the molecule, and the following general formula (1) A monomer mixture (A) containing a (meth) acrylic acid ester monomer (c);
(Meth) acrylic acid ester copolymer (B), which is a copolymer of monomers including the monomers (a), (b) and (c) in the monomer mixture (A);
An isocyanate compound (C) represented by the following general formula (2);
A photopolymerization initiator (D);
A tackifying resin (F) that is a polymer of a polymerizable monomer containing a (meth) acrylic acid ester monomer;
A laminate characterized by the above.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, n represents an integer of 0 to 6, and a plurality of n may be mixed.)
(Chemical formula 2)
^{NCO-R 2 -NHCOO-P-} NHCOO-R 3 -OCN (2)
(In the formula, R ² represents a residue obtained by removing an isocyanate group from a diisocyanate compound having two NCO groups in the molecule, and R ³ is a residue obtained by removing the isocyanate group from a diisocyanate compound having two NCO groups in the molecule. And P represents a residue obtained by removing a hydroxyl group from a diol compound having two OH groups in the molecule.)   2. The laminate according to claim 1, wherein the foam base material comprises at least one selected from the group consisting of urethane foam and ethylene / propylene / diene rubber (EPDM) foam.   Content of the isocyanate compound (C) is 100 parts by mass in total of the monomer mixture (A), the (meth) acrylic acid ester copolymer (B), and the photopolymerization initiator (D). The laminate according to claim 1, wherein the laminate is 1 part by mass to 5 parts by mass.   The polymerizable monomer (b) having a nitrogen atom in the molecule is at least one of N-vinylpyrrolidone and dimethylaminoethyl methacrylate, according to any one of claims 1 to 3. Laminated body.   The (meth) acrylic acid ester copolymer (B) has a weight average molecular weight (Mw) of 200,000 to 400,000, and a ratio (Mw) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). / Mn) has a dispersity of 2.0 to 5.0 and has 3 to 10 mol of polymerizable double bonds per mol of copolymer molecules in the side chain. The laminated body in any one of.   The polymerizable double bond of the side chain of the (meth) acrylic acid ester copolymer (B) is glycidyl acrylate or glycidyl methacrylate, the monomer (a) in the monomer mixture (A), The laminate according to claim 5, wherein the laminate is introduced by reacting with a copolymer of monomers containing (b) and (c).   The laminate according to any one of claims 1 to 6, wherein the photocurable pressure-sensitive adhesive composition further contains chlorinated polypropylene (E).   The laminate according to any one of claims 1 to 7, wherein the tackifying resin (F) has a weight average molecular weight (Mw) of more than 20,000 and 150,000 or less.   The laminate according to any one of claims 1 to 8, wherein the tackifying resin (F) is a polymer having no polymerizable double bond. The photocurable pressure-sensitive adhesive composition is curable with ultraviolet rays having an irradiation intensity of 10 to 1,000 mW / cm ² and an integrated light amount of 10 to 1,000 mJ / cm ^2. The laminated body of crab. It is a manufacturing method of the laminated body which manufactures the laminated body in any one of Claim 1 to 10, Comprising: Irradiation intensity 10-1,000 mW / cm < ² >, integrated light quantity 10-are given to the said photocurable adhesive composition. The manufacturing method of the laminated body characterized by including the ultraviolet irradiation process of irradiating the ultraviolet-ray of 1,000 mJ / cm < ² >.

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