TW201638286A - Photocurable adhesive composition - Google Patents

Abstract

The present invention is a photocurable adhesive composition which provides a laminate having the same adhesive strength when irradiated with light in the presence of oxygen as when in the absence of oxygen, said composition containing: (A) a (meth)acrylate oligomer having at least four functional groups and a molecular weight of 10,000-70,000; (B) a monofunctional (meth)acrylate monomer; (C) a photoreaction initiator; (D) a tackifier having a softening point of 70-150 DEG C; and (E) a liquid plasticizer.

Description

Photohardenable composition

The present invention relates to a photocurable composition, a laminate using the same, an optical display using the same, and a method for producing a laminate.

In recent years, an image display device such as a smart phone has a display body such as a liquid crystal display panel or an organic EL panel and a touch panel directly from the viewpoint of preventing deterioration of visibility due to surface reflection. The bonding of the front panel of the display body and the protective panel or the bonding of the touch panel to the front panel is performed for bonding or for reinforcement. In the method of producing an image display device, there is known a method in which a photocurable resin composition is applied to a substrate on one side of a target, and then irradiated with ultraviolet rays to form a photocurable resin. The temporarily hardened resin layer of the article is bonded to the substrate on the other side (Patent Document 1).

However, the radical polymerization type of the acrylic resin which is widely used in the photocurable resin composition is poor in surface hardenability due to inhibition of oxygen in the air, so that the surface remains as an insufficiently hardened component on the surface. This has the problem that the subsequent strength is lowered. In this regard, Patent Document 2 discloses a method of decompressing an inert gas such as nitrogen or the like. The photocurable resin composition containing a polyisoprene methacrylate oligomer, dicyclopentenyloxyethyl methacrylate, and lauryl methacrylate was irradiated with ultraviolet rays in an atmosphere.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-151151

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2013-254189

However, in the method described in Patent Document 2, in order to eliminate the influence of the hardening inhibition by oxygen, it is necessary to introduce a device for providing a reduced pressure or an inert gas atmosphere.

Accordingly, the present invention has been made to solve the above problems, and an object of the present invention is to provide a photocurable type subsequent composition which is equivalent to a case where oxygen is not present even in the case where light is irradiated in the presence of oxygen. The strength of the laminate is then followed.

The present invention has the following constitution.

[1] A photocurable type subsequent composition comprising: (A) a tetrafunctional or higher (meth) propyl group having a molecular weight of 10,000 to 70,000 Ethylenate oligomer, (B) monofunctional (meth) acrylate monomer, (C) photoreaction initiator, (D) tackifier having a softening point of 70 to 150 ° C, and (E) liquid Plasticizer.

[2] The photocurable type subsequent composition according to [1] above, wherein the component (A) is selected from the group consisting of (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, and polyamine group. One or more of the group of (meth) acrylate oligomers having an acid ester structure.

[3] The photocurable composition of the above [1] or [2], wherein the component (B) is selected from the group consisting of an alkyl (meth) acrylate and a hydroxy-substituted alkyl (meth) acrylate. One or more of the group.

[4] A laminate obtained by laminating the photocurable composition of any one of the above [1] to [3].

[5] The laminate according to the above [4], which is an optical display.

[6] A method for producing a laminated body comprising the following steps (I) to (III): (I) the photocuring type of any one of the above [1] to [3] The substrate is applied to the substrate 1 to form a photocurable type followed by the composition layer; (II) the photocurable type of the composition layer obtained in the step (I) is irradiated with an energy ray to form a photohardenable type followed by hardening of the composition. And (III) a step of attaching the substrate 2 to the cured product obtained in the step (II).

[7] The production method according to [6] above, wherein the step (II) is formed The photocuring type of the cured product has a reaction rate of 90% or more.

According to the present invention, it is possible to provide a photocurable composition which is a laminate which is equivalent to the strength when oxygen is not present even when light is irradiated in the presence of oxygen.

[Best Mode for Carrying Out the Invention]

(photohardening type follow-up composition)

The photocurable type subsequent composition contains: (A) a tetrafunctional or higher (meth) acrylate oligomer having a molecular weight of 10,000 to 70,000, (B) a monofunctional (meth) acrylate monomer, and (C) light. The reaction initiator, (D) a tackifier having a softening point of 70 to 150 ° C, and (E) a liquid plasticizer.

<(A) A tetrafunctional or higher (meth) acrylate oligomer having a molecular weight of 10,000 to 70,000>

(A) a tetrafunctional or higher (meth) acrylate oligomer having a molecular weight of 10,000 to 70,000 (hereinafter also referred to as "(A) oligomer") having 4 or more (meth) acrylonitrile in a molecule base. In the present specification, "(meth) acrylate" includes both "acrylate" and "methacrylate". Further, "(meth)acryloyl group" includes both "acryloyl fluorenyl group" and "methacryl fluorenyl group".

(A) The oligomer has a molecular weight of 10,000 to 70,000, and more preferably 20,000 to 50,000. When the molecular weight of the oligomer is less than 10,000, the modulus of elasticity tends to increase and the flexibility tends to decrease. When the molecular weight of the oligomer exceeds 70,000, the viscosity increases and the workability tends to decrease. In the present specification, the molecular weight is a weight average molecular weight measured by gel permeation chromatography (GPC) and converted using a test line of standard polystyrene.

(A) The number of functional groups of the oligomer (the number of (meth)acrylinyl groups) is 4 or more, preferably 4 to 10, more preferably 4 to 6, and particularly preferably 4. When the number of functional groups of the oligomer is 3 or less, when the light is irradiated in the presence of oxygen, the hardening inhibition by oxygen becomes remarkable, and the strength is lowered. In addition, when the number of the functional groups of the (A) oligomer is 10 or less, when the light is irradiated in the presence of oxygen, the increase in the modulus of elasticity accompanying the increase in the number of functional groups can be suppressed.

(A) The oligomer is not particularly limited, and for example, a (meth) acrylate oligomer having (hydrogenated) polyisoprene, (hydrogenated) polybutadiene or a polyurethane in the skeleton is used. These (meth) acrylate oligomers can be used in one type or two types or more. Here, the (hydrogenated) polyisoprene is composed of polyisoprene and/or hydrogenated polyisoprene, and the (hydrogenated) polybutadiene is composed of polybutadiene and/or hydrogenated polybutadiene.

(Meth) acrylate oligomers having (hydrogenated) polybutadiene in the skeleton, such as (hydrogenated) polybutadiene (meth) acrylate, and (hydrogenated) polybutadienyl urethane (Meth) acrylate.

(meth)acrylic acid having (hydrogenated) polyisoprene in the skeleton The ester oligomers are, for example, (hydrogenated) polyisoprene (meth) acrylate, and (hydrogenated) polyisoprene urethane (meth) acrylate.

a (meth) acrylate oligomer having a polyurethane in the skeleton, such as a polyether type, a polycarbonate type, a polyester type, or a combination of the polyurethane (meth) acrylate Ester oligomer. A commercially available product of the (A) (meth) acrylate oligomer having a polyurethane in the skeleton is, for example, UV-7610B (manufactured by Nippon Synthetic Chemical Co., Ltd.; molecular weight: 11,000, hexafunctional).

(A) The oligomer preferably has a (hydrogenated) polybutadiene in the skeleton, and is preferably a urethane (meth)acrylic acid modified (hydrogenated) polybutadiene. (A) The oligomer may be used alone or in combination of two or more.

<<(A) Method for producing oligomers>>

(A) The oligomer can be produced by a method described in, for example, JP-A-2014-189758 or JP-A-2002-309185. Further, the (A) oligomer can be produced by a method of condensing a hydroxyl group-containing resin with (meth)acrylic acid, and a method of transesterifying a (meth) acrylate with a hydroxyl group-containing resin. . Further, the (A) oligomer can be specifically produced by a method including "a step of obtaining a prepolymer having an isocyanate group" and a "step of obtaining a (meth) acrylate oligomer" The "step of obtaining a prepolymer having an isocyanate group" is a (hydrogenated) polybutadiene having a hydroxyl group, a (hydrogenated) polyisoprene having a hydroxyl group; and being selected from a polyester containing a hydroxyl group, a hydroxyl group-containing resin composed of a hydroxyl group-containing polyether and a hydroxyl group-containing polycarbonate; and a polyisocyanate The reaction is carried out to obtain a prepolymer having an isocyanate group; the "step of obtaining a (meth) acrylate oligomer" is a prepolymer having an isocyanate group and a (meth)acrylic acid having a hydroxyl group The ester reacts with the (meth) acrylate oligomer. Hereinafter, "hydroxyl-containing resin", "polyisocyanate", "hydroxyl-containing (meth) acrylate, and "(meth) acrylate" will be described.

<<<Resin containing hydroxyl>>>

The hydroxyl group-containing resin is a raw material resin of a (meth) acrylate oligomer, and examples thereof include (hydrogenated) polybutadiene containing a hydroxyl group, (hydrogenated) polyisoprene having a hydroxyl group, polyester containing a hydroxyl group, and containing a polyether of a hydroxyl group and a polycarbonate containing a hydroxyl group. The hydroxyl group-containing resin is preferably a (hydrogenated) polybutadiene having a hydroxyl group at both terminals, a (hydrogenated) polyisoprene having a hydroxyl group at both terminals, and a polyester having a hydroxyl group at both terminals, at both ends. A polyether having a hydroxyl group and a polycarbonate having a hydroxyl group at both terminals. Thus, it can be introduced into a (meth) acrylonitrile group having 1 or more ends at both ends, and preferably a (meth) acryl fluorenyl group having 2 or more at both ends.

Examples of the (hydrogenated) polybutadiene having a hydroxyl group at both terminals include GI-3000 (manufactured by Nippon Soda Co., Ltd.), GI-1000 (manufactured by Nippon Soda Co., Ltd.), G-3000 (manufactured by Nippon Soda Co., Ltd.), and Poly bd ( Idemitsu Kosan Co., Ltd.). Examples of the (hydrogenated) polyisoprene having a hydroxyl group at both terminals include, for example, Poly ip (manufactured by Idemitsu Kosan Co., Ltd.). Examples of the polyester having a hydroxyl group at both terminals, a polyether having a hydroxyl group at both terminals, and a polycarbonate having a hydroxyl group at both terminals are, for example, Polylite OD-X-2251 (manufactured by DIC Corporation). PPG (manufactured by Mitsui Chemicals, Inc.), Duranol T5652 (manufactured by Asahi Kasei Chemicals Co., Ltd.), Preminol 4004, Preminol 4015 (manufactured by Asahi Glass Co., Ltd.), Adeka polyether P-3000, Adeka new ace V14-90 (manufactured by Adeka Co., Ltd.), etc. It is commercially available and can be used depending on the molecular weight or polarity of the object, and is not particularly limited.

<<<Polyisocyanate>>>

The polyisocyanate is not particularly limited as long as it is a compound having two or more isocyanate groups, and examples thereof include an aromatic, aliphatic or alicyclic polyisocyanate.

Aromatic polyisocyanates, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, four Methyl phthalic acid diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and the like.

An alicyclic polyisocyanate such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis(isocyanatomethyl) ring Hexane, etc.

The aliphatic polyisocyanate may, for example, be hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diazonic acid diisocyanate, leucine triisocyanate or the like.

<<<Hydroxy-containing (meth) acrylate>>>

The (meth) acrylate containing a hydroxyl group is not particularly limited as long as it is a (meth) acrylate compound having one or more hydroxyl groups and one or more (meth) acrylonitrile groups in the molecule. Hydroxy-containing (meth) acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylic acid 4-hydroxybutyl ester, 2-(methyl)propenyloxyethyl-2-hydroxypropyl phthalate, caprolactone modified 2-hydroxyethyl (meth)acrylate, cyclohexyl a (meth) acrylate having one hydroxyl group and one (meth) acrylonitrile group in a molecule such as alkane dimethanol mono(meth)acrylate; 2-hydroxy-3-(methyl) propylene oxime One of hydroxyl groups and two or more molecules in the molecule such as methoxypropyl (meth) acrylate, neopentyl alcohol tri(meth) acrylate, and dipentaerythritol penta (meth) acrylate A (meth) acrylate (meth) acrylate or the like.

The (A) oligomer can be obtained by adjusting the number of hydroxyl groups of the hydroxyl group-containing resin and the number of (meth)acryloyl groups in the hydroxyl group-containing (meth) acrylate. The combination of the hydroxyl group-containing resin and the hydroxyl group-containing (meth) acrylate is not particularly limited as long as the obtained oligomer has 4 or more (meth) acrylonitrile groups in the molecule. The combination of the hydroxyl group-containing resin and the hydroxyl group-containing (meth) acrylate may, for example, be a combination of a hydroxyl group-containing resin and a hydroxyl group-containing (meth) acrylate, that is, the hydroxyl group-containing resin has both ends. The one hydroxyl group-containing resin and the hydroxyl group-containing (meth) acrylate are (meth) acrylate compounds having one hydroxyl group and one or more (meth) acrylonitrile groups.

<<<(Meth)acrylate>>>

The (meth) acrylate is not particularly limited as long as it is a (meth) acrylate compound having one or more (meth) acrylonitrile groups in the molecule and having no hydroxyl group. As such a compound, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate An alkyl ester of (meth)acrylic acid such as ester, lauryl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate or isostearyl (meth)acrylate; An aralkyl ester of (meth)acrylic acid such as benzyl methacrylate; cyclohexyl (meth)acrylate, isodecyl (meth) acrylate, dicyclopentenyl (meth) acrylate, etc. An alicyclic ester of (meth)acrylic acid; a heterocyclic ester of (meth)acrylic acid such as tetrahydroindenyl (meth) acrylate;

The conditions of the amount of use of each component, the reaction temperature, and the reaction time are not particularly limited as long as the (A) oligomer can be obtained, and can be appropriately selected.

<(B) Monofunctional (meth) acrylate monomer>

(B) The monofunctional (meth) acrylate monomer is not particularly limited as long as it is a (meth) acrylate compound having one (meth) acrylonitrile group in the molecule. (B) a monofunctional (meth) acrylate monomer, for example, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (methyl) Alkyl (meth)acrylic acid such as tributyl acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, isodecyl (meth) acrylate Ester; (meth)acrylic acid methoxy b An alkoxy-substituted alkyl (meth) acrylate such as an ester; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ( a hydroxy-substituted alkyl (meth) acrylate such as 4-hydroxybutyl methacrylate; 2-(meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2- Hydroxy-3-(methyl)propenyloxypropyl (meth) acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate, cyclohexane dimethanol mono (meth) acrylate a hydroxyl group-containing (meth) acrylate other than a hydroxy-substituted alkyl (meth) acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, etc.; dicyclopentenyloxyethyl ( Methyl) acrylate, norbornene (meth) acrylate, dicyclopentenyl (meth) acrylate, isodecyl (meth) acrylate, and the like. (B) The monofunctional (meth) acrylate monomer is preferably one or more selected from the group consisting of alkyl (meth) acrylates and hydroxy-substituted alkyl (meth) acrylates.

(B) The monofunctional (meth) acrylate monomer may be used alone or in combination of two or more. When two or more (B) monofunctional (meth) acrylate monomers are used in combination, a combination of an alkyl (meth) acrylate and a hydroxy-substituted alkyl (meth) acrylate is preferred.

(B) The monofunctional (meth) acrylate monomer is preferably from 1 to 250 parts by mass, more preferably from 20 to 200 parts by mass, even more preferably from 30 to 200 parts by mass per part by mass of the (A) oligomer. 150 parts by mass, particularly preferably 40 to 90 parts by mass.

<(C) Photoreaction Starter>

(C) Photoreaction starter is not particularly limited, and examples thereof include 1-[4-(2-hydroxyl) Ethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-one, benzophenone, 2,2-dimethoxy -1,2-diphenylethane-1-one, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2,4,6-trimethylbenzhydrylphenylethoxy Phosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1, 2-hydroxy-2-methyl-1-phenyl-propane-1 -ketone, 2-methyl-1-[4-methylthio]phenyl]-2-morpholinylpropan-1-one, benzoin methyl ether, benzoin ethyl ether, benzoin Butyl ether, benzoin isopropyl ether, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2-hydroxy-2-methyl-[4-(1-A Ethyl vinyl) phenyl] propanol oligomer, 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomer, 2-hydroxy-2-methyl -1-phenyl-1-propanone, isopropyl thioxanthone, methyl o-benzoyl benzoate, [4-(methylphenylthio)phenyl]phenylmethane, 2,4-diethyl Thiophenone, 2-chlorothioxanthone, benzophenone, ethyl hydrazine, benzophenone ammonium salt, thioxanthone ammonium salt, bis(2,6-dimethoxybenzylidene) -2,4,4-trimethyl-pentylphosphine oxide, bis(2,6-dimethoxy Benzobenzyl)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4'- Bis-diethylaminobenzophenone, 1,4-dibenzoylphenyl, 10-butyl-2-chloroacridone, 2,2'bis(o-chlorophenyl)4,5,4 ',5'-肆(3,4,5-trimethoxyphenyl) 1,2'-biimidazole, 2,2'bis(o-chlorophenyl)4,5,4',5'-four Phenyl-1,2'-biimidazole, 2-benzylidene naphthalene, 4-benzylidenebiphenyl, 4-benzylidene diphenyl ether, benzoated benzophenone, bis (η 5 -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, o-methylbenzhydrylbenzene Formate, ethyl p-dimethylaminobenzoate, isoamyl ethyl p-dimethylaminobenzoate, active tertiary amine, carbazole benzophenone photoreaction initiator, acridine Photoreaction initiation A photocatalyst, a triazine-based photoreaction initiator, a benzamidine-based photoreaction initiator, and the like.

(C) a photoreaction initiator which is selected from the group consisting of 1-hydroxy-cyclohexyl-phenyl-ketone and 2,4,6-trimethylbenzimidylphenylethoxyphosphine oxide One or more kinds are preferred.

(C) The photoreaction initiator may be used alone or in combination of two or more.

(C) The photoreaction initiator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, still more preferably 1 to 10 parts by mass, per 100 parts by mass of the (A) oligomer.

<(D) Adhesive with a softening point of 70 to 150 ° C>

The photocurable type of the following composition contains (D) an adhesive having a softening point of 70 to 150 ° C (hereinafter also referred to as "(D) tackifier"). By the photocurable type, the composition contains (D) a tackifier, and then the strength is increased, and at the same time, the hardened material can be softened, and the followability to the object can be improved.

(D) The softening point of the tackifier is preferably 75 to 130 ° C, more preferably 80 to 120 ° C from the viewpoint of strength and flexibility. The softening point is a value measured by the ring and ball method.

The (D) tackifier may be exemplified by a rosin ester resin such as a heterogeneous rosin ester, a polymerized rosin ester or a (hydrogenated) rosin ester; an acrylic polymer, an acrylic copolymer, etc., as long as the softening point is satisfied. Acrylic resin; polyoxynene resin; terpene resin such as terpene resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin; thermoplastic elastomer; petroleum resin; alicyclic saturated hydrocarbon group Resin; rosin-based resin such as rosin; xylene resin, and the like.

(D) The tackifier is preferably a rosin ester resin, and a hydrogenated rosin ester is further preferred. The rosin ester-based resin is esterified by the carboxylic acid moiety of the rosin, and it is possible to suppress the influence of the acid component on the object (for example, the wiring portion of the touch panel or the like). Further, the hydrogenated rosin ester can also prevent coloring at the initial stage and when exposed to heat due to hydrogenation of the rosin. (D) The adhesive may be used alone or in combination of two or more.

The amount of the (D) tackifier may be 5 to 70% by mass based on 100% by mass of the photocurable composition. As long as it is within this range, the amount of the reaction component is appropriate, whereby good film properties can be obtained, and the effect of exhibiting the strength of the adhesion is also advantageous. The tackifier is preferably 100 to 60% by mass, more preferably 15 to 50% by mass, based on 100% by mass of the photocurable composition.

<(E) Liquid plasticizer>

The photocurable type of subsequent composition comprises (E) a liquid plasticizer. The fluidity exhibited at 25 ° C in a liquid system at atmospheric pressure is, for example, a cone-and-plate viscometer, and exhibits a viscosity of 1,000 Pa ‧ or less (for example, 0.01 to 1,000 Pa‧ s viscosity). When the photocurable type subsequent composition contains (E) a liquid plasticizer, a cured product having a small modulus of elasticity and a softness can be obtained.

As the (E) liquid plasticizer, dibutyl phthalate, diisononyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, Phthalate esters such as diisononyl phthalate and butyl benzyl phthalate; dioctyl adipate and diisoindole adipic acid A polycarboxylic acid alkyl ester such as an ester, dioctyl sebacate, diisononyl sebacate, diisodecyl 1,2-cyclohexanedicarboxylate (for example, a C3 to C12 alkane of a polycarboxylic acid) a phosphate ester such as a cresyl phosphate or a tributyl phosphate; an alkyl ester of a polyoxyalkylene glycol such as a trimellitate or a triethylene glycol bis(2-ethylhexanoate); (for example, C3~C12 alkyl ester of di-, tri- or tetraethylene glycol, etc.); rubber-based polymer, rubber-based copolymer (for example, polyisoprene, polybutadiene or polybutene, or Such a hydride, a derivative in which a hydroxyl group is introduced at both ends or a derivative in which a hydroxyl group is introduced into both ends of the hydride, etc.); a thermoplastic elastomer; a petroleum resin; an alicyclic saturated hydrocarbon-based resin; Terpene resin such as olefin resin, terpene phenol resin, modified terpene resin or hydrogenated terpene resin; rosin resin such as rosin; heterogeneous rosin ester resin, polymerized rosin ester resin, (hydrogenated) A rosin ester resin such as a rosin ester resin; a xylene resin or the like; an acrylic resin such as an acrylic polymer or an acrylic copolymer. These may be in the form of a liquid.

The (E) liquid plasticizer is preferably a rosin ester resin (but may be in the form of a liquid), and preferably hydrogenated rosin ester (but may be in the form of a liquid). (E) The liquid plasticizer may be used alone or in combination of two or more.

The liquid plasticizer (E) can be set to an amount of 300 parts by mass or less based on 100 parts by mass of the (D) tackifier, from the viewpoint of exhibiting strength by the (D) adhesive. From the viewpoint of strength and flexibility, it is preferably from 10 to 250 parts by mass, more preferably from 30 to 200 parts by mass, still more preferably from 50 to 150 parts by mass.

<further ingredients>

In the photocurable type of the subsequent composition, the composition, the antioxidant, the antifoaming agent, the pigment, the filler, the chain lock transfer agent, the light stabilizer, and the surface tension can be blended in a range that does not impair the effects of the present invention. Adjusting agent, leveling agent, ultraviolet absorber, foam suppressant, etc. Further, one component may be used alone or two or more types may be used in combination. The total content of the further component is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, still more preferably 1 to 5 parts by mass, per 100 parts by mass of the (A) oligomer.

<Photosetting method of photocuring type subsequent composition>

The photocurable type of the composition can be prepared by mixing the components. The method of mixing is not particularly limited, and various metals, plastic containers, stirring blades, and agitator can be used.

<Use of photocuring type and subsequent composition>

The photocurable type of the subsequent composition can be used for bonding any of the substrate 1 and any of the substrates 2. The substrate 1 and the substrate 2 may be the same substrate or may be different substrates. At least one of the substrate 1 and the substrate 2 may be a light transmissive member. As a result, an energy ray (for example, ultraviolet ray) is applied to the photocurable type subsequent composition from the light permeable member side to form a cured resin layer. As the light transmissive member, glass, (meth)acrylic resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimine, polyester, cycloolefin polymer can be exemplified. Wait.

The photo-curing type is followed by a composition for bonding the display body to the touch panel, the display body and the front panel, or the use of the touch panel and the front panel. good. The optical display body can be obtained by bonding the display body and the touch panel, the display body and the front panel, or the touch panel to the front panel using the photocurable type subsequent composition.

As the front panel, glass or engineering plastics, for example, acrylic sheets (either hard coating or AR coating on one or both sides), transparent plastic sheets such as polycarbonate sheets, PET sheets, and PEN sheets can be exemplified. . The front panel can also be used as a protective panel. As the touch panel, a resistive film type, an electrostatic capacity type, an electromagnetic induction type, or an optical touch panel can be exemplified. As the display body, an LCD, an EL display, an EL illumination, an electronic paper, a plasma display, or the like can be exemplified. The front panel, the touch panel, and the display system may have a step or may have a light blocking portion. Here, the light-shielding portion means a portion which does not have an energy ray (for example, ultraviolet ray) required for the photocuring type subsequent coating applied on the subsequent surface to be cured by irradiation.

(laminate)

The laminate obtained by laminating with a photocurable type of subsequent composition is also an object of the present invention. Specifically, the laminate system is obtained by laminating an arbitrary substrate 1 and an arbitrary substrate 2 with a photocurable composition. The method for producing the laminate is not particularly limited, but a method for producing a laminate to be described later is preferable. Further, it is preferable to use an optical display body by laminating the resultant obtained by photocuring a composition.

(Manufacturing method of laminate)

The manufacturing method of the laminate is the substrate 1 and the substrate 2, which are interspersed with light hard. A method for producing a laminate obtained by laminating a cured product of a composition, and comprising the following steps (I) to (III): (I) applying a photocurable composition to a substrate 1 to form a step of photocuring followed by a composition layer; (II) a step of irradiating the photohardenable layer of the photocurable layer obtained in the step (I) with an energy ray to form a cured product of the photocurable type of the subsequent composition; and (III) The step of bonding the substrate 2 to the cured product obtained in the step (II).

In the method for producing a laminate, the photocurable subsequent composition, the substrate 1 and the substrate 2 are preferably in a preferred embodiment as described above. Therefore, the method of producing the laminate is preferably a method of producing an optical display. Further, the laminate system obtained by the method for producing a laminate is preferably an optical display.

<Step (I)>

Step (I) is a step in which a photocurable type subsequent composition is applied to the substrate 1 to form a photocurable type followed by a composition layer.

The method of applying the photocurable composition to the substrate 1 is not particularly limited, and a method such as a die coater, a dispenser, or screen printing can be used. The thickness of the photocurable type subsequent composition layer is not particularly limited, and may be, for example, 10 to 500 μm, and preferably 30 to 350 μm.

<Step (II)>

Step (II) is a photo-curing type of the composition layer obtained by the step (I) The energy line is irradiated to form a step of photohardening type followed by hardening of the composition.

The energy line is not particularly limited, and an active energy ray such as visible light, ultraviolet light, X-ray, or electron beam can be used. The energy line is preferably ultraviolet light. As a light source of ultraviolet rays, a light source that emits ultraviolet rays (UV) can be used. Examples of the light source of the ultraviolet light include a metal halide lamp, a high pressure mercury lamp, a xenon lamp, a mercury xenon lamp, a halogen lamp, a pulsed xenon lamp, and an LED. The peak wavelength of the LED is not particularly limited, and examples thereof include 365 nm, 405 nm, 375 nm, 385 nm, and 395 nm. Light emitted from a light source other than the LED can be adjusted to light of a specific wavelength by an optical filter. Specifically, it can be adjusted by an optical filter that blocks light having a wavelength of 300 nm or less and/or an optical filter that blocks light of a wavelength of 500 nm or more.

The irradiation of the energy ray is performed so that the cumulative light amount of the energy ray becomes 30 to 15,000 mJ/cm ² . The cumulative amount of light is preferably from 50 to 12,000 mJ/cm ^{2 , and more} preferably from 100 to 10,000 mJ/cm ² .

In the step (II), the energy ray is irradiated from the photocurable type on the side of the composition to form a cured resin layer. Here, when the base material 1 is a light transmissive member, the energy ray may be irradiated from the light permeable member side to the photocurable type subsequent composition to form a cured resin layer.

The reaction rate of the photocurable subsequent composition in the cured product formed in the step (II) is not particularly limited, and is preferably 90% or more. When the reaction rate is 90% or more, even if no further irradiation is performed after the bonding, the step can be simplified by exhibiting sufficient strength. Moreover, there is no need to worry about the photohardenable type of the composition which remains without being hardened. The penetration or damage of the member, the exudation from the hardened material, can also be applied to the case where the opaque light-shielding layer is provided on the laminate or the substrate which is completely opaque. The reaction rate is defined by the rate of decrease of the (meth) acrylonitrile group in the photocurable type of the composition before and after the irradiation with an energy ray (for example, ultraviolet ray), and can be measured by FT-IR. In addition, the case where the (meth) acrylonitrile group in the photocurable type subsequent composition was all reacted was set to 100%.

<Step (III)>

The step (III) is a step of attaching the substrate 2 to the cured product obtained in the step (II) to obtain a laminate. On the substrate 1 on which the cured product is formed, the substrate 2 is placed in contact with the cured product, and the substrate 1 and the substrate 2 can be bonded together. The substrate 2 is a substrate to which the photocurable subsequent composition is not applied in the step (I).

The method for producing a laminate may further include a step of pressurizing a laminate comprising a base material 1 and a base material 2 and a cured product of the photocurable type composition and the like. The manufacturing method of the laminate is carried out by including a pressure treatment, thereby further improving the adhesion strength of the laminate. The pressurization treatment can be carried out using a rubber roller, a flat plate pressing device, or the like.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. The invention is not limited by these examples. Unless otherwise specified, the mass parts and mass % are shown.

Evenly mixing the ingredients shown in Table 1 to The photocurable type of the composition of the comparative example and the comparative example was prepared. Here, polybutadienyl urethane acrylates A to F were produced in accordance with the following Synthesis Examples 1 to 6.

Synthesis Example 1 (Production of Polybutadiene Aurethane Acrylate A)

Hydrogenated polybutadiene (GI-3000, manufactured by Nippon Soda Co., Ltd., number average molecular weight) was placed in a four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with a drying tube. 3,000, iodine value 21, hydroxyl value 25 to 35 mgKOH/g) 300 g (molecular weight calculated by using a hydroxyl group value of 30 mgKOH: 0.080 mol), p-methoxyphenol 0.1 g as a polymerization inhibitor, and tin as a catalyst Dibutyltin dilaurate (manufactured by Tokyo Fine Chemical Co., Ltd., L101) 0.1 g. After the temperature was raised to 80 ° C, 30.2 g (0.136 mol) of isophorone diisocyanate (Desmodur I, manufactured by Bayer Urethane Co., Ltd.) was uniformly dropped over 1 hour. After the completion of the dropwise addition, the reaction was carried out at 80 ° C for 3 hours. Thereafter, 11.5 g (0.080 mol) of 4-hydroxybutyl acrylate (4-HBA, manufactured by Nippon Kasei Co., Ltd.) was added. After the reaction at 80 ° C for 4 hours, it was confirmed by FT-IR that the absorption at the absorption wavelength (2270 nm) of the isocyanate disappeared and the reaction was terminated, and the hydrogenated polybutadiene and isophorone diisocyanate were obtained as the repeating unit. And a polyurethane acrylate oligomer having an average functional group number of 2 having a polymerizable unsaturated bond at the terminal. The resulting hydrogenated polybutadiene skeleton polyurethane acrylate had a weight average molecular weight of 12,000. Further, the weight average molecular weight is measured by GPC and converted to a value converted from a test line of standard polystyrene.

Synthesis Example 2 (Production of Polybutadienylurethane acrylate B)

In the same manner as in Synthesis Example 1, except that the amount of isophorone diisocyanate was 26.7 g (0.120 mol), a polyurethane having an average functional group number of 2 and a weight average molecular weight of 26,000 was obtained. Acrylate oligomer.

Synthesis Example 3 (Production of Polybutadienylurethane acrylate C)

A polyurethane having an average functional group number of 2 and a weight average molecular weight of 43,000 was obtained in the same manner as in Synthesis Example 1, except that the amount of isophorone diisocyanate was 23.1 g (0.104 mol). Acrylate oligomer.

Synthesis Example 4 (Production of Polybutadienylurethane acrylate D)

In addition to 2-hydroxy-3-propenyl propyl methacrylate (NK ester 701A, manufactured by Shin-Nakamura Chemical Co., Ltd.) was set to 17.1 g (0.080 mol) and replaced with 4-hydroxybutyl acrylate, and Synthesis Example 2 In the same manner, a polyurethane acrylate oligomer having an average functional group number of 4 and a weight average molecular weight of 24,000 was obtained.

Synthesis Example 5 (manufacture of polybutadienyl urethane acrylate E)

A polyurethane having an average functional group number of 4 and a weight average molecular weight of 36,000 was obtained in the same manner as in Synthesis Example 4 except that the amount of isophorone diisocyanate was 24.9 g (0.112 mol). Acrylate Oligomer.

Synthesis Example 6 (Production of Polybutadienylurethane acrylate F)

A polyurethane having an average functional group number of 4 and a weight average molecular weight of 42,000 was obtained in the same manner as in Synthesis Example 4 except that the amount of isophorone diisocyanate was 23.1 g (0.104 mol). Acrylate oligomer.

Using the obtained photohardenable composition of the comparative example and the comparative example, the characteristics were measured as follows.

<elasticity>

Elasticity: A No. 3 dumbbell-shaped test piece (thickness: 1 mmt) was produced in accordance with JIS Z1702, and measured by a tensile compression tester (manufactured by Minebea, Techno graph TG-2kN) at a speed of 10 mm/min. In addition, the dumbbell-type test piece was produced by using a conveyor type metal halide lamp (200 mW/cm ² manufactured by Eye Graphics Co., Ltd.) and hardening the photocurable type-attached composition at 6,000 mJ/cm ² .

<OPEN intensity and CLOSE intensity>

A test piece of OPEN strength and CLOSE strength as described below was obtained.

<<OPEN hardening strength test piece>>

The coated portion of the photocurable type of the composition was formed to have a width of 20 mm, and the substrate 1 (26 mm × 75 mm × 1.1 mmt, glass) was used to adhere the prepared 150 μ mt thickness using three pieces of celec ribbon (50 μ mt). The spacer was coated with a photocurable type-substrate layer using a metal squeegee to form a photo-curing type subsequent composition layer, and then a belt-type metal halide lamp (200 mW/cm ² manufactured by Eye Graphics Co., Ltd.) was used at 3,000 mJ/ The cm ² is irradiated with light from the photo-curing type and then on the side of the composition layer to form a cured product of the photo-curing type and then the composition. The base material 3 (26 mm × 150 mm × 0.1 mm t, PET) was placed on the cured product of the photocurable type-attachable composition and joined to obtain an OPEN-hardened strength measurement test piece.

<<CLOSE hardening strength test piece>>

On the substrate 1 (26 mm × 75 mm × 1.1 mmt, glass), the coated portion of the photocurable type-substrate was formed to have a width of 20 mm, and three pieces of cellophane tape (50 μm) were used to adhere the prepared 150 μm. After the spacer of the thickness is applied and the photo-curing type composition is applied using a metal squeegee to form a photo-curing type subsequent composition layer, the substrate 2 (26 mm × 75 mm × 0.05 mmt, release PET) is placed on the photo-curing type. After the bonding on the composition layer, the substrate was irradiated with light at 3,000 mJ/cm ² by a conveyor-type metal halide lamp (200 mW/cm ² manufactured by Eye Graphics Co., Ltd.) to form a photocurable composition. Hardened matter. The base material 2 was peeled off, and the base material 3 (26 mm × 150 mm × 0.1 mm t, PET) was placed on the surface of the peeled substrate 2 and joined, whereby a CLOSE-hardened strength measurement test piece was obtained.

<<Measurement of OPEN strength and CLOSE intensity>>

The OPEN strength and the CLOSE strength were measured by a tensile compression tester (manufactured by Minebea, Techno graph TG-2kN) at a speed of 300 mm/min.

<intensity change rate>

The intensity change rate of the above OPEN intensity and CLOSE intensity can be obtained. When the intensity change rate is 20% or less, it is evaluated as "○", and when it exceeds 20%, it is evaluated as "X".

<reaction rate>

In the cured product of the photocurable type subsequent composition, the reaction rate of the photocurable type of the subsequent composition is the rate of reduction of the acrylonitrile group before and after the irradiation of the energy line of the photocurable type composition, by FT-IR (Perkin ELmer) The company system, Spectrum 100) to carry out the measurement. The reduction rate is obtained by substituting the following formula (1) and substituting the absorption peak height (X) of 800 to 820 cm ^-1 from the baseline in the FT-IR measurement spectrum of the photo-curing type composition layer before the energy ray irradiation, It can be obtained from the absorption peak height (Y) of 800 to 820 cm ^-1 from the baseline in the FT-IR measurement spectrum of the cured product of the photocurable type subsequent composition after irradiation with the energy ray.

Reaction rate (%) = {(X-Y) / X} × 100‧‧‧(1)

<<Measurement of hardening rate of OPEN hardening>>

On the substrate 1 (26 mm × 75 mm × 1.1 mmt, glass), the coated portion of the photocurable type-substrate was formed to have a width of 20 mm, and three pieces of cellophane tape (50 μm) were used to adhere the prepared 150 μm. After the spacer of the thickness and the photocurable type of the composition were applied by using a metal squeegee, the photocurable type subsequent composition layer was formed by a conveyor type metal halide lamp (200 mW/cm ² manufactured by Eye Graphics Co., Ltd.) at 3,000 mJ. /cm ² is irradiated with light from the photocurable type and then on the side of the composition layer to form a cured product of the photocurable type and then the composition. The base material 3 (26 mm × 150 mm × 0.1 mm t, PET) was placed on the cured product of the photocurable type-attachable composition and joined to obtain an OPEN-hardened strength measurement test piece. The reaction rate of the photocurable composition was measured for the cured product of the photocurable subsequent composition in the strength test piece of the OPEN hardening.

<<Measurement of hardening rate of CLOSE hardening>>

On the substrate 1 (26 mm × 75 mm × 1.1 mmt, glass), the coated portion of the photocurable type-substrate was formed to have a width of 20 mm, and three pieces of cellophane tape (50 μm) were used to adhere the prepared 150 μm. After the spacer of the thickness is applied and the photo-curing type composition is applied using a metal squeegee to form a photo-curing type subsequent composition layer, the substrate 2 (26 mm × 75 mm × 0.05 mmt, release PET) is placed on the photo-curing type. After the bonding on the composition layer, the substrate was irradiated with light at 3,000 mJ/cm ² by a conveyor-type metal halide lamp (200 mW/cm ² manufactured by Eye Graphics Co., Ltd.) to form a photocurable composition. Hardened matter. The base material 2 was peeled off, and the base material 3 (26 mm × 150 mm × 0.1 mm t, PET) was placed on the surface of the peeled substrate 2 and joined, whereby a CLOSE-hardened strength measurement test piece was obtained. The cured product of the photocurable type subsequent composition in the strength test piece of CLOSE hardening was measured, and the reaction rate of the photocurable type subsequent composition was measured.

The results are summarized in Table 1.

The intensity change rate of Examples 1 to 3 was 0 (i.e., there was no difference in strength between OPEN hardening and CLOSE hardening). In other words, by including a tetrafunctional or higher (meth) acrylate oligomer, even when light is irradiated in the presence of oxygen, the bonding strength is equivalent to that in the absence of oxygen. On the other hand, Comparative Examples 1 to 3 do not contain a tetrafunctional or higher (meth) acrylate oligomer, and are in the presence of oxygen as compared with the subsequent strength when irradiated with light in the absence of oxygen. The adhesion strength when irradiated with light is lowered.

[Industry Utilization]

The photocurable subsequent composition is a laminate, and is particularly suitable as an adhesive for an optical display and an optical display.

Claims (7)

A photocurable type subsequent composition comprising: (A) a tetrafunctional or higher (meth) acrylate oligomer having a molecular weight of 10,000 to 70,000, and (B) a monofunctional (meth) acrylate monomer; C) a photoreaction initiator, (D) a tackifier having a softening point of 70 to 150 ° C, and (E) a liquid plasticizer. The photocurable type following composition of claim 1, wherein the component (A) is selected from the group consisting of (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, and polyurethane in the skeleton ( One or more of the group of the methyl acrylate oligomers. The light-curing type composition according to claim 1 or 2, wherein the component (B) is one or more selected from the group consisting of an alkyl (meth) acrylate and a hydroxy-substituted alkyl (meth) acrylate. . A laminate obtained by laminating the photocurable type of the composition of any one of claims 1 to 3. A laminate according to claim 4, which is an optical display. A manufacturing method of a method for producing a laminate comprising the following steps (I) to (III): (I) applying the photocurable composition of any one of claims 1 to 3 to a substrate 1, a step of forming a photo-curing type followed by a composition layer; (II) a step of irradiating the photo-curable type of the layer of the photocurable layer obtained in the step (I) with an energy ray to form a cured product of the photo-curing type and then the composition; (III) a step of attaching the substrate 2 to the cured product obtained in the step (II). The production method according to claim 6, wherein the photocuring type of the cured product formed in the step (II) has a reaction rate of 90% or more.