JP6021715B2 - Photo-curable adhesive composition - Google Patents

Description

  The present invention relates to a photocurable pressure-sensitive adhesive composition.

Generally, an isocyanate curing agent or the like is added to an adhesive composition containing a base polymer such as a synthetic rubber in order to improve cohesion (holding power) and heat resistance (for example, Patent Document 1). To 3).
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 2002-241709 A JP 2001-49200 A JP 2011-46961 A

  In the pressure-sensitive adhesive compositions described in these Patent Documents 1 to 3, the cohesive force and heat resistance of the pressure-sensitive adhesive composition are improved by increasing the crosslinking density of the pressure-sensitive adhesive composition by adding an isocyanate curing agent. However, there was a problem that the throwing ability and the curved surface followability deteriorated.

  Then, the objective of this invention is providing the photocurable adhesive composition which can improve anchoring property and curved surface followability, improving cohesion force and heat resistance.

The photocurable pressure-sensitive adhesive composition of the present invention comprises a monomer mixture (A), a (meth) acrylic acid ester copolymer (B), a predetermined isocyanate compound (C), and a photopolymerization initiator (D ).
According to this configuration, in the photocurable pressure-sensitive adhesive composition, the active hydrogen group (for example, the isocyanate group in the predetermined isocyanate compound (C) is present in the side chain of the (meth) acrylate copolymer (B). , Hydroxyl group, carboxyl group, amino group, etc.) to form a cross-linked structure to improve the cohesive strength and heat resistance of the photocurable pressure-sensitive adhesive composition, while the anchoring property and curved surface followability of the photocurable pressure-sensitive adhesive composition Can be improved. 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.

  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, the said photocurable adhesive composition is a polymer of the polymerizable monomer containing a (meth) acrylic acid ester monomer, and a weight average molecular weight (Mw) exceeds 20,000 150,000. When the tackifying resin (F) which is the following is further included, the tackiness can be improved while maintaining the compatibility of the components.

  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.

  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 contributing to polymerization such as a carbon-carbon double bond, and (vi) “weight average molecular weight (Mw)” is NCO in the isocyanate compound (C). % (Measured by JIS K1603-1B method), (vii) “number average molecular weight (Mn)” is NCO% in isocyanate compound (C) (measured by JIS K1603-1B method) Based on (Viii) “number of moles of polymer” means the weight of the obtained polymer divided by the weight average molecular weight, and (ix) “mol of polymerizable double bond”. “Number” means the number of moles of the reacted compound, and (x) “residue obtained by removing isocyanate group from diisocyanate compound having two NCO groups in the molecule” means, for example, 1 to 80 carbon atoms. Means a carbon bond part (hydrocarbon), and (xi) “residue obtained by removing a hydroxyl group from a diol compound having two OH groups in the molecule” means, for example, a carbon bond part having 1 to 80 carbon atoms ( Hydrocarbon).

  ADVANTAGE OF THE INVENTION According to this invention, the photocurable adhesive composition which can improve anchoring property and curved surface followability can be provided, improving cohesion force and heat resistance.

FIG. 1 is a schematic diagram for explaining a method for evaluating adhesiveness (tackiness). FIG. 2 is a schematic diagram for explaining a method for producing an evaluation sample used for evaluation of tackiness (tackiness). FIG. 3 is a schematic diagram for explaining a method for evaluating adhesiveness (throwing property). FIG. 4 is a schematic diagram for explaining a method for producing an evaluation sample used for evaluation of adhesiveness (throwing property). FIG. 5 is a schematic diagram for explaining a method for producing an evaluation sample used for evaluating the presence or absence of curing inhibition. FIG. 6 is a schematic diagram for explaining a method for evaluating the cohesive force (holding force). FIG. 7 is a schematic diagram for explaining an evaluation method of heat resistance (high temperature side softening point). FIG. 8 is a schematic diagram for explaining a method for evaluating water resistance (hot water peeling test). FIG. 9 is a schematic diagram for explaining a method for evaluating curved surface followability.

(Photocurable adhesive composition)
The photocurable pressure-sensitive adhesive composition of 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, if necessary, other components.

<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.

-(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, tackiness (initial tackiness) may be reduced, and it exceeds 5.0. In some cases, the cohesive force is insufficient, and the adhesive performance such as holding power 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) can be appropriately selected according to the amount of the polymerizable double bond in the side chain, but the monomer mixture (A) and the (meth) acrylic acid ester copolymer (B) and the mixture are 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.

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. In the production of acrylate copolymer from acrylate monomer, sudden and intense heat generation may occur, leading to reaction runaway. If it exceeds 50 mol times, bulk polymerization can be carried out safely. The polymerization rate may be slow and the production time may be long.

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) 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)
^{O = C = N-R 2} -NHCOO-P-OOCHN-R 3 -N = C = O (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 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, etc.) present in the side chain of the acrylate copolymer (B) in the photocurable pressure-sensitive adhesive composition. And a cross-linked 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 JIS K1603-1 B 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.

<Photopolymerization initiator (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.

<Other ingredients>
The photocurable pressure-sensitive adhesive composition of the present invention is a chlorinated polypropylene (E); a tackifying resin (F); calcium carbonate, aluminum hydroxide, silica, 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; A dye, a pigment, a polymerization inhibitor, a stabilizer, 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). .

-Tackifying 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

  The weight average molecular weight (Mw) of the tackifying resin (F) is not particularly limited as long as it is more than 20,000 and not more than 150,000, and can be appropriately selected according to the purpose. ~ 137,000 is preferable, 37,000 to 137,000 is more preferable, and 37,000 to 60,000 is particularly preferable. When the weight average molecular weight (Mw) of the tackifying resin (F) is 20,000 or less, the tackiness is lowered, and when it is more than 150,000, the compatibility of the components is lowered. On the other hand, when the molecular weight of the tackifying resin (F) is within a preferable range, more preferable range, or particularly preferable range, the molecular weight of the tackifying resin (F) is too small. As a result, the entanglement between the (meth) acrylic acid ester copolymer (B) and the tackifier resin (F) can be easily unraveled, and the adhesive property can be reliably prevented from being deteriorated. When the molecular weight of the imparting resin (F) is too large, the (meth) acrylic acid ester copolymer (B) and the tackifying resin (F) are less likely to be entangled and the adhesive properties are deteriorated. This is advantageous in that it can be surely 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 of (meth) acrylic acid ester, so the monomer ((meth) acrylic acid ester monomer (a), (meth) acrylic acid ester in the monomer mixture (A) It dissolves well in the 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.

  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 analysis values and characteristics shown in Tables 1 to 7 were measured by the following methods.

-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). The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the (meth) acrylic acid ester copolymer (B) are shown in Table 1, and the weight average molecular weight (Mw) of the tackifier resin (F) is shown in Table 2. Shown in
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.

-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.

-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). The results are shown in Table 2.

-Compatibility (Photocurable adhesive composition)-
The compatibility of the photocurable pressure-sensitive adhesive composition was evaluated by visual confirmation. The evaluation criteria are as follows. The results are shown in Tables 3-7.
-Evaluation criteria-
○: Tackifying resin compatible x: Tackifying resin incompatible-: Tackifying resin not contained

-Adhesiveness (tackiness) (photo-curable adhesive composition)-
As shown in FIG. 1, the evaluation sample 100 of 25 mm × 25 mm × 10 mm produced by the production method shown in FIG. 2 below is completely closed on a stainless steel support plate 110 having a hole with a diameter of 11.4 mm, In addition, after the release paper 200 has been peeled off, the adhesive plate 230 is pasted so that the cured adhesive layer 230 side becomes the stainless steel support plate 110 side, and then the support plate is formed only by the weight of the stainless steel weight 120 having a weight of 10 g and a bottom surface of 11.4φ. A probe that measures the maximum value of the force when the weight is pulled up at a speed of 300 mm / min after passing through the hole (13φ) and sticking to the adhesive layer 230 and holding for 10 seconds and holding for 10 seconds. By performing the tack test under the following conditions, the tackiness (tackiness) of the photocurable pressure-sensitive adhesive composition was evaluated. The evaluation criteria are as follows. The results are shown in Tables 3 to 7.
-Evaluation sample preparation method-
As shown in FIG. 2, an area of 100 mm × 150 mm and a film thickness of 60 μm ± are applied to the release paper 200 by using a variable bar coater with the photocurable adhesive composition of each composition (Tables 3 to 7). Coating is carried out to 5 μm to form a pressure-sensitive adhesive layer (uncured) 210 (pressure-sensitive adhesive coating), and irradiation environment under a nitrogen atmosphere (oxygen concentration of 1,000 ppm) from the pressure-sensitive adhesive layer (uncured) 210 side Then, UV220 was irradiated (UV irradiation) so that the irradiation intensity was 100 mW / cm ² and the integrated light amount was 150 mJ / cm ^2, and the pressure-sensitive adhesive layer was cured to form a pressure-sensitive adhesive layer (cured) 230. Thereafter, the foam base material 240 having a thickness of 10 mm is bonded to the pressure-sensitive adhesive layer (cured) 230 side (the foam base material is bonded), and then pressed once under the pressure-bonding condition in which the compressibility in the thickness direction is 50% ( Crimping), and after crimping, the sample 100 was allowed to stand at room temperature for 24 hours to produce an evaluation sample 100.
--- Probe tack test conditions ---
Equipment used: STA-1150 (made by ORIENTEC)
Sample size: 25mm x 25mm
Curing time after base material pressure bonding: 24 hours Load: Stainless steel weight Test load: 10 g Weight weight Bottom diameter: 11.4 mm
Load contact time: 10 seconds Tensile speed: 300 mm / min Test environment: 23 ° C., 50%
Measured value: Maximum pulling force-Evaluation criteria-
☆: 45N / mm ² more than ◎: 35N / mm ² ultra-45N / mm ² or less ○: 25N / mm ² ultra-35N / mm ² or less △: 5N / mm ² ultra-25N / mm ² or less ×: 5N / mm ² or less -: Evaluation not possible

-Adhesiveness (throwing property) (photo-curable adhesive composition)-
As shown in FIG. 3, an evaluation sample 300 of 25 mm × 150 mm produced by the production method shown in FIG. 4 is used, and STA-1150 manufactured by ORIENTEC is used to attach the evaluation sample “foaming substrate 310” to one chuck A. Between the foam substrate 310 and the pressure-sensitive adhesive layer 350 at 300 mm / minute, and sandwich the “core material 320 + pressure-sensitive adhesive layer (one layer) 330 + release paper 340” between the other chucks B. Then, from the point where the peeling behavior was stabilized, the adhesiveness (throwing property) of the photocurable pressure-sensitive adhesive composition was evaluated by taking the integral average value up to 150 mm as a measured value. The evaluation criteria are as follows. The results are shown in Tables 3-7.
-Evaluation sample preparation method-
As shown in FIG. 4, an area of 100 mm × 150 mm and a film thickness of 60 μm ± are applied to the release paper 340 by using a variable bar coater for the photocurable adhesive composition of each composition (Tables 3 to 7). 5 μm is applied to form an adhesive layer (uncured) 345 (first adhesive application), and from the adhesive layer (uncured) 345 side under a nitrogen atmosphere (oxygen concentration 1,000 ppm) In an irradiation environment, UV 360 is irradiated so that the irradiation intensity is 100 mW / cm ² and the integrated light amount is 150 mJ / cm ² (first UV irradiation), and the pressure-sensitive adhesive layer (uncured) 345 is cured and pressure-sensitive adhesive layer ( Cured) 330 was formed. Thereafter, the roller 370 is reciprocated once to bond the core material 320 made of a nonwoven fabric (core material bonding), and the photocurable adhesive of each composition (Tables 3 to 7) on the bonded core material 320. The adhesive composition is applied using a variable bar coater so that the area is 100 mm × 150 mm and the film thickness is 60 μm ± 5 μm to form an adhesive layer (uncured) 390 (second adhesive application) From the pressure-sensitive adhesive layer (uncured) 390 side, UV400 is irradiated so that the irradiation intensity is 100 mW / cm ² and the integrated light amount is 150 mJ / cm ² (second UV irradiation), and the pressure-sensitive adhesive layer (uncured) 390 was cured to form an adhesive layer (cured) 350. Thereafter, a foam base material 310 having a thickness of 10 mm is bonded to the pressure-sensitive adhesive layer (cured) 350 side, and then crimped once (crimping) under a crimping condition in which the compression rate in the thickness direction is 50%. The evaluation sample 300 was produced by leaving it at room temperature for a period of time.
-Test conditions-
Equipment used: STA-1150 (made by ORIENTEC)
Sample size: 25mm x 150mm
Curing time after base material pressure bonding: 24 hours Peeling speed: 300 mm / min Test environment: 23 ° C., 50%
Measured value: From the point where the peeling behavior is stable, the integrated average value up to 150 mm--evaluation criteria--
◎: More than 4N / 25mm ○: More than 3N / 25mm 4N / 25mm or less △: More than 1N / 25mm or less than 3N / 25mm ×: Less than 1N / 25mm-: Evaluation not possible

-Presence or absence of curing inhibition (photo-curable adhesive composition)-
For the evaluation sample produced by the production method shown in FIG. 5 below, the curing rate is calculated from the reduction rate of the carbon-carbon double bond peak (810 cm ⁻¹ ) of the adhesive by the following measurement method using FT-IR. Thus, the presence or absence of inhibition of curing of the photocurable pressure-sensitive adhesive composition was evaluated. The evaluation criteria are as follows. The results are shown in Tables 3-7.
-Evaluation sample preparation method-
As shown in FIG. 5, an area of 100 mm × 150 mm and a film thickness of 60 μm ± are applied to the release paper 500 by using a variable bar coater with the photocurable adhesive composition of each composition (Tables 3 to 7). Coating is carried out to 5 μm to form an adhesive layer (uncured) 510 (adhesive application), and the irradiation environment under a nitrogen atmosphere (oxygen concentration of 1,000 ppm) from the adhesive layer (uncured) 510 side Then, UV520 is irradiated so that the irradiation intensity is 100 mW / cm ² and the integrated light amount is 150 mJ / cm ² (UV irradiation), and the pressure-sensitive adhesive layer (uncured) 510 is cured to form the pressure-sensitive adhesive layer (cured) 530. An evaluation sample was prepared.
--Measurement method of cure rate--
FT-IR Nicolet 6700 manufactured by Thermo Fisher Scientific Co., Ltd. was used to measure the curing rate of several tens of microns on the surface. The measurement method and measurement conditions are as follows.
・ Measurement method: ATR method (one reflection)
・ Resolution: 8cm ^-1
-Accumulated number: 32 times The curing rate was calculated from the amount of change in the peak area of the C = CH out-of-plane variable vibration of 810 cm ^-1 with reference to the C = O symmetric stretching vibration near 1720 cm ^-1 according to the following equation.
(Equation 3)
Curing rate (%) = (1- (810 cm ⁻¹ peak area after curing / 1720 cm ⁻¹ peak area after curing) / (810 cm ⁻¹ peak area before curing / 1720 cm ⁻¹ peak area before curing)) × 100
-Evaluation criteria-
○: Curing rate over 95% Δ: Curing rate over 90% to 95% or less ×: Curing rate 90% or less

-Cohesive strength (holding power) (photo-curable adhesive composition)-
As shown in FIG. 6, the prepared sample is cut into 25 mm × 50 mm in the same manner as the evaluation sample used for adhesiveness (tackiness) (as shown in FIG. 2). 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. 6) to dropping (B in FIG. 6) 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 Tables 3-7. The test environment was a temperature of 23 ° C. and a humidity of 50%.
-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. 7, the prepared sample is cut into 25 mm × 50 mm in the same manner as the evaluation sample used for adhesiveness (tackiness) (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 hanging the load (weight) 740 (A in FIG. 7) to dropping (B in FIG. 7) as a measured value, using a 3D BANK SHEAR TESTER manufactured by Chemistments, The heat resistance of the curable adhesive composition was evaluated. The evaluation criteria are as follows. The results are shown in Tables 3-7. 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. 8, the prepared sample is cut into 25 mm × 350 mm in the same manner as the evaluation sample used for adhesiveness (tackiness) (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. 8). Next, the foaming substrate / adhesive interface was peeled off at 300 mm / min, and from the point where the peeling behavior was stabilized, by taking the integrated average value up to 100 mm as the measured value,
A heat resistant water peeling test was performed using ORIENTEC STA-1150 to evaluate the water resistance of the photocurable pressure-sensitive adhesive composition. The evaluation criteria are as follows. The results are shown in Tables 3-7.
-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

−Curved surface followability (photo-curable adhesive composition) −
As shown in FIG. 9, the produced sample is cut into 25 mm × 120 mm in the same manner as the evaluation sample used for adhesiveness (tackiness) (as shown in FIG. 2). Next, the 15 mm × 120 mm region of the cut evaluation sample 900 is bonded to a PP plate 910 having an L shape as an adherend and each surface being 100 mm × 100 mm. Next, the bonded portion (5 mm × 120 mm) is pressed and pressed with a finger and left at room temperature for 24 hours. Next, the evaluation sample 900 is immersed in an oven at 80 ° C. for 24 hours. The presence or absence of peeling of the evaluation sample 900 is judged visually. The evaluation criteria are as follows. The results are shown in Tables 3-7.
-Evaluation criteria-
○: no peeling after 60 minutes ×: peeling after 60 minutes −: evaluation not possible

<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 tackifier resin having the composition and physical properties shown in Table 2 was further polymerized using a partially polymerized syrup prepared as described below, so that the polymerization rate was 100%.
-Preparation of partially polymerized syrup-
As a polymerizable monomer, a monomer or a monomer mixture shown in Table 2 is charged as a polymerizable monomer into a 2-liter four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube and a 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 under stirring and reacted for 30 minutes to obtain a partially polymerized syrup.

However, in Table 2, “CHMA” represents “cyclohexyl methacrylate (Tg: 66 ° C.)”, “IBOA” represents “isobornyl acrylate (Tg: 88 ° C.)”, and “MMA” represents “methyl” Methacrylate (Tg: 105 ° C.) ”,“ TBMA ”represents“ tert-butyl methacrylate (Tg: 107 ° C.) ”,“ TCDA ”represents“ tricyclodecanyl acrylate (Tg: 120 ° C.) ”, “TCDMA” indicates “tricyclodecanyl methacrylate (Tg: 175 ° C.)”, and “IBOMA” indicates “isobornyl methacrylate (Tg: 180 ° C.)”.

Each component was mix | blended with the prescription shown in Table 3-Table 7 (the value in each component represents a mass part), and the photocurable adhesive composition was prepared. And by the above-mentioned method, the compatibility, tackiness (tackiness), tackiness (throwing property), presence / absence of curing inhibition, cohesive force (holding force), heat resistance, water resistance, curved surface followability are measured and evaluated. went. The results are shown in Tables 3 to 7. In Tables 3 to 7, “Actual” indicates an example (for example, “Actual 1” indicates Example 1), “Ratio” indicates a comparative example (for example, “Ratio 1” indicates a comparative example) 1).
In Tables 3 to 7, “−” means “not evaluated” because the compatibility of the tackifier resin is poor.

In Tables 3 to 7, 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 ′)
L-75C: Death Module L-75 (C) (manufactured by Sumika Bayer Urethane Co., Ltd .: TMP adduct body represented by the following formula (3))
HL: Coronate HL (manufactured by Nippon Polyurethane Industry Co., Ltd .: TMP adduct represented by the following formula (3))
N3200: Death module N3200 (manufactured by Sumika Bayer Urethane Co., Ltd .: burette body represented by the following formula (4))
IL1351: Death module IL1351 (manufactured by Sumika Bayer Urethane Co., Ltd .: isocyanurate represented by the following formula (5))
HX: Coronate HX (Nippon Polyurethane Industry Co., Ltd .: isocyanurate represented by the following formula (5))
(Iii) 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)
E-15: Desmodur E-15 (manufactured by Sumika Bayer Urethane Co., Ltd .: prepolymer type tolylene diisocyanate (TDI) (aromatic isocyanate) represented by the above formula (2), weight average molecular weight (Mw) : 800-1000)
E-21-1: Sumidur E-21 (manufactured by Sumika Bayer Urethane Co., Ltd .: prepolymer type diphenylmethane diisocyanate (MDI) (aromatic isocyanate) represented by the above formula (2), weight average molecular weight (Mw) ): 200-300)
SBU0620: SBU isocyanate 0620 (manufactured by Sumika Bayer Urethane Co., Ltd .: prepolymer type diphenylmethane diisocyanate (MDI) (aromatic isocyanate) represented by the above formula (2), weight average molecular weight (Mw): 400 to 500)
E-23: Desmodur E-23 (manufactured by Sumika Bayer Urethane Co., Ltd .: prepolymer type diphenylmethane diisocyanate (MDI) (aromatic isocyanate) represented by the above formula (2), weight average molecular weight (Mw): 200-300)

(In the formula, R ⁴ represents a residue obtained by removing an isocyanate group from a diisocyanate compound having two NCO groups in the molecule. The plurality of R ⁴ may be the same or different. )

(In the formula, R ⁵ represents a residue obtained by removing an isocyanate group from a diisocyanate compound having two NCO groups in the molecule. The plurality of R ⁵ may be the same or different. )

(Wherein, R ⁶ represents a residue obtained by removing the isocyanate groups from a diisocyanate compound having two NCO groups in the molecule. Further, a plurality of R ⁶ may each be the same or different. )
(Iv) Photopolymerization initiator (D)
・ Lucirin TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by BASF Japan ・ IRGACURE 184: 1-hydroxycyclohexyl phenyl ketone, manufactured by chiba (v) chlorinated polypropylene (E)
DX-530P: Toyobo Co., Ltd. chlorinated polypropylene DX-523P: Toyobo Co., Ltd. Chlorinated polypropylene (vi) Tackifying resin (F)
-Tackifying resins T-1 to T-11: those obtained in Synthesis Examples 5 to 15 described above

  From Tables 3 to 7, the (meth) acrylic acid ester monomer (a) having an alkyl group having 4 or more carbon atoms, the polymerizable monomer (b) having a nitrogen atom in the molecule, and the above general formula A monomer mixture (A) containing the (meth) acrylic acid ester monomer (c) represented by (1), and the monomers (a) and (b) in the monomer mixture (A) ) And (c), a (meth) acrylic acid ester copolymer (B), an isocyanate compound (C) represented by the above general formula (2), and photopolymerization start It can be seen that the photocurable pressure-sensitive adhesive compositions of Examples 1 to 25 containing the agent (D) can improve anchoring properties and curved surface followability while improving cohesion and heat resistance. .

  Moreover, Examples 1-25 using the isocyanate compound (C) (prepolymer type isocyanate compound) represented by the said General formula (2) are comparative examples using the isocyanate compound (C ') of a TMP adduct body. Unlike the comparative example 3 which used the isocyanate compound (C ') of 1 and 2 and a burette body, and the comparative examples 4-5 which used the isocyanate compound (C') of the isocyanurate body, a long-chain carbon bond part Since the isocyanate compound (C) having (P in the above general formula (2)) is used, it can be seen that the anchoring property and the curved surface followability can be improved, and it is excellent.

  Moreover, Examples 1-25 using the isocyanate compound (C) (prepolymer type isocyanate compound) represented by the said General formula (2) are comparative examples using the isocyanate compound (C ') of a TMP adduct body. In the same manner as in Comparative Examples 3 and 2, Comparative Example 3 using a burette isocyanate compound (C ′), and Comparative Examples 4 to 5 using an isocyanurate isocyanate compound (C ′), a base polymer (monomer Since the active hydrogen group (for example, hydroxyl group, carboxyl group, amino group, etc.) of the mixture (A) and (meth) acrylic acid ester copolymer (B)) reacts with the terminal isocyanate group (NCO group), It can be seen that the cohesive force and heat resistance can be improved, which is excellent.

  Moreover, Examples 16-25 using the isocyanate compound (C) (prepolymer type isocyanate compound) represented by the general formula (2) and the tackifier (F) are based on a base polymer (monomer mixture ( A) and (meth) acrylic acid ester copolymer (B) mixture), isocyanate compound (C) and tackifier (F). It can be seen that the water resistance can be improved and the water resistance can be improved. In addition, regarding cohesive strength (holding power) and heat resistance (softening point), the influence of the isocyanate compound (C) is large. Regarding anchoring property and water resistance, both the isocyanate compound (C) and the tackifier (F) are used. There is an influence.

100 Evaluation Sample 110 Stainless Steel Support Plate 120 Stainless Steel Weight 200 Release Paper 210 Adhesive Layer (Uncured)
220 UV
230 Adhesive layer (cured)
240 Foam base material 300 Evaluation sample 310 Foam base material 320 Core material 330 Adhesive layer (cured)
340 Release paper 345 Adhesive layer (uncured)
350 Adhesive layer (cured)
360 UV
370 Roller 390 Adhesive layer (uncured)
400 UV
500 Release paper 510 Adhesive layer (uncured)
520 UV
530 Adhesive layer (cured)
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 900 Evaluation Sample 910 PP Plate

Claims (8)

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);
And a photopolymerization initiator (D). A photocurable pressure-sensitive adhesive composition comprising:
(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)
^{O = C = N-R 2} -NHCOO-P-OOCHN-R 3 -N = C = O (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.)   The content of the isocyanate compound (C) is 100 parts by mass in total of the monomer compound (A), the (meth) acrylic acid ester copolymer (B), and the photopolymerization initiator (D). The photocurable pressure-sensitive adhesive composition according to claim 1, wherein the composition is 1 part by mass to 5 parts by mass.   The photocurable property according to claim 1 or 2, wherein the polymerizable monomer (b) having a nitrogen atom in the molecule is at least one of N-vinylpyrrolidone and dimethylaminoethyl methacrylate. Adhesive composition.   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 photocurable pressure-sensitive adhesive composition according to any one of the above.   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 photocurable pressure-sensitive adhesive composition according to claim 4, which is introduced by reacting with a copolymer of monomers containing (b) and (c).   The photocurable pressure-sensitive adhesive composition according to any one of claims 1 to 5, wherein the photocurable pressure-sensitive adhesive composition further comprises chlorinated polypropylene (E).   The photocurable pressure-sensitive adhesive composition is a polymer of a polymerizable monomer containing a (meth) acrylic acid ester monomer, and has a weight average molecular weight (Mw) of more than 20,000 and not more than 150,000 The photocurable pressure-sensitive adhesive composition according to claim 1, further comprising an imparting resin (F).   The photocurable pressure-sensitive adhesive composition according to claim 7, wherein the tackifying resin (F) is a polymer having no polymerizable double bond.