KR20190120239A - Active energy ray-curable adhesive composition for plastic film or sheet - Google Patents

Abstract

Providing the active energy ray hardening-type adhesive composition for plastic films or sheets which is excellent in sclerosis | hardenability, is excellent in the adhesive force to various plastic films or sheets which contained the cellulose film and (meth) acrylic-type resin, and was excellent also in colorless transparency. The present invention is (A) component: aromatic epoxy compound having a weight average molecular weight of 500 or more, (B) component: polyglycidyl ether of polyol having 2 to 10 carbon atoms, (C) component: compound having alicyclic epoxy group, (D) component: As a composition containing a photocationic polymerization initiator, the content ratio of the said (A)-(D) component is the whole composition (A) component: 1-30 weight%, (B) component: 20- It relates to 70 weight%, (C) component: 10-60 weight%, (D) component: 0.5-10 weight% active energy ray hardening-type adhesive composition for plastic films or sheets.

Description

Active energy ray-curable adhesive composition for plastic film or sheet

The present invention relates to an active energy ray-curable adhesive composition capable of adhering various plastic films or sheets by irradiation of active energy rays such as ultraviolet rays, visible light, or electron beams, and also used in liquid crystal displays, organic EL displays, and the like. It is used suitably for manufacture of the various optical films or sheets which are used, and what is commercially available in these technical fields.

In addition, in this specification, acrylic resin and / or methacryl-type resin are (meth) acrylic-type resin, acrylate and / or methacrylate are (meth) acrylate, acryloyl group, and / or methacryloyl group Is a (meth) acryloyl group and acrylic acid and / or methacrylic acid are represented by (meth) acrylic acid.

In addition, below, when it is not necessary to specifically state, a plastic film or sheet is collectively represented by "plastic films", and a film or sheet is collectively represented by "films."

Conventionally, in the laminating method of adhering thin adherends of plastic films or thin adherends of plastic films and thin adherends made of different materials, a solvent type comprising an ethylene-vinyl acetate copolymer or a polyurethane-based polymer After apply | coating an adhesive composition to a 1st thin layer to-be-adhered body, and drying it, the dry lamination method which crimps | bonds a 2nd thin-layer to-be-adhered body with a nip roller etc. is mainly performed.

The adhesive composition used in this method generally contains a large amount of solvent in order to make the composition uniform, but for this reason, a large amount of solvent vapor is volatilized during drying, which causes toxicity, work safety and environmental pollution. It is becoming.

A solvent-free adhesive composition is examined as an adhesive composition which solves these problems.

As a non-solvent type adhesive composition, the active-energy-ray-curable adhesive composition hardened | cured by active energy rays, such as a two-component adhesive composition and an ultraviolet-ray or an electron beam, is widely used.

As a two-component adhesive composition, what is called a polyurethane adhesive composition mainly uses the polymer which has a hydroxyl group at the terminal, and uses the polyisocyanate compound which has an isocyanate group at the terminal as a hardening | curing agent. However, the composition has the drawback that it takes a long time to cure.

On the other hand, the active energy ray-curable adhesive composition is used in recent years because of its high curing rate and excellent productivity.

On the other hand, various displays such as liquid crystal displays and organic EL displays are thin, light, and power-saving, so that mobile devices, personal computers, TVs, and the like that are equipped with touch panels such as mobile phones, smartphones, tablets, and car navigation systems, etc. It is widely used for medium and large image display devices such as digital signage. The active energy ray-curable adhesive composition is also widely used for the attachment of various optical films used in liquid crystal displays and organic EL displays.

Examples of the optical films include hard coat films to which functions such as fingerprint prevention and non-gloss are provided, front panels of touch panels, polarizing plates, retardation films, viewing angle compensation films, brightness enhancement films, antireflection films, antiglare films, lens sheets, and diffusion sheets. These etc. are mentioned, Various kinds of plastics are used for these.

Among these plastics, cellulose films such as triacetyl cellulose and (meth) acrylic resins such as polymethyl methacrylate are widely used because they are particularly excellent in optical properties such as colorless transparency and optical isotropy.

Background Art In recent years, the spread of capacitive touch panels has replaced most mobile phones with smartphones, and new products such as tablets have become widespread. Moreover, the market share of organic electroluminescent display is increasing by the performance improvement of organic electroluminescent display. As such, the display of the mobile device is still evolving, but at that time, the configuration of the optical films may be changed. At this time, there is a case where the necessity of adhering a plastic material having completely different surface properties may be imposed. For example, cellulose-based films such as triacetyl cellulose and (meth) acrylic-based resins such as polymethyl methacrylate are plastic materials widely used for optical applications, but the surface properties of the two are different. There is also a demand for an active energy ray-curable adhesive that is excellent in transparency, which strongly adheres both to such a dissimilar material and does not generate yellowing or opacity after curing.

In addition, in a mobile device, thinning and weight reduction are important issues, and therefore, it is required to reduce the thickness of the adhesive. In order to coat an adhesive thin, the viscosity reduction of an adhesive composition becomes important. By the way, when it is going to make the active energy ray hardening-type adhesive agent of a solvent low viscosity, the urethane (meth) acrylate generally used in the active energy ray hardening-type adhesive agent of a (meth) acrylate is difficult to use because its viscosity is high. For this reason, it was difficult to make both low viscosity and strong adhesive force compatible with a (meth) acrylate type adhesive agent.

In addition, when at least one of a to-be-adhered body is a film, although strong peeling adhesive force is required in many cases, in order to strengthen this peeling adhesive force, it is necessary to enlarge the tan-delta of the dynamic-viscoelasticity measurement of adhesive hardened | cured material, and to thicken an adhesive agent. It is effective (nonpatent literature 1). In other words, it is difficult to make the film thickness of an adhesive agent 3 micrometers or less, and to strengthen peeling adhesive force.

Patent Literature 1 discloses a photocationic curable adhesive containing a polyfunctional aliphatic epoxy monomer as a main component, and containing an alicyclic epoxy monomer and / or an oxetane monomer, even if the thickness of the adhesive is thin, such as cycloolefin polymer or triacetyl cellulose. It is disclosed that the adhesion to the plastic material is excellent.

Patent Document 1: Japanese Patent Application Laid-Open No. 2008-63397 (claims)

Non-Patent Document 1: Minato Moto-Nori, Adhesion, Vol. 47, No. 8, pages 12-15 (2003)

However, the active energy ray hardening-type adhesive composition disclosed by patent document 1 has a problem that it is inferior to productivity because cationic sclerosis | hardenability is bad and energy required for hardening is large. For this reason, it is necessary to slow down the line speed of the bonding process or to increase the number of light sources, and it was difficult to express sufficient adhesive force even at an irradiation amount of 200 mJ / cm 2 or less under UV-B (near 310 nm).

Moreover, according to the examination result of this inventor, the composition disclosed by patent document 1 had the problem that the adhesive force to (meth) acrylic-type resins, such as a polymethyl methacrylate and an alkyl (meth) acrylate polymer, is inadequate.

This invention is made | formed in view of the said problem, and is excellent in sclerosis | hardenability, and the adhesive force to various plastic films containing (meth) acrylic-type resins, such as cellulose films, such as a triacetyl cellulose, and polymethylmethacrylate, Another object is to provide an active energy ray-curable adhesive composition for plastic films that is excellent in colorless transparency.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the said subject, As a result, the weight average molecular weight is the aromatic epoxy compound of 500 or more, the polyglycidyl ether of the polyol which has C2-C10, the compound which has an alicyclic epoxy group, and photocationic polymerization. The active-energy-ray-curable adhesive composition containing an initiator in a specific ratio each discovered that the said subject was solved, and completed this invention.

The present invention is (A) component: aromatic epoxy compound having a weight average molecular weight of 500 or more, (B) component: polyglycidyl ether of polyol having 2 to 10 carbon atoms, (C) component: compound having alicyclic epoxy group , (D) component: As a composition containing a photocationic polymerization initiator, the content ratio of said (A)-(D) component is the whole composition (A) component: 1-30 weight%, (B) component: 20 to 70% by weight, (C) component: 10 to 60% by weight, (D) component: 0.5 to 10% by weight of the active energy ray-curable adhesive composition for plastic films.

As (A) component, the compound whose weight average molecular weights are 1,000-20,000, and the number of epoxy groups contained in 1 molecule is 2 or more is preferable, and it is more preferable that it is a bisphenol A type epoxy resin and / or a bisphenol F type epoxy resin.

As the component (B), diglycidyl ether of diol having 2 to 6 carbon atoms is preferable, and diglycidyl ether of alkanediol having 4 to 6 carbon atoms is more preferable.

As (C) component, the compound which has an alicyclic epoxy group shown by following formula (1) is preferable.

As (D) component, a sulfonium salt type photocationic polymerization initiator is preferable.

As a content rate of (A)-(D) component, 3 to 20 weight% of (A) component, 30 to 60 weight% of (B) component, and 20 to 50 weight% of (C) component in the whole composition, ( It is preferable that 1-5 weight% of D) components are included, (B) component is 100 weight part, content of (A) component is less than 100 weight part, and content of (C) component is less than 100 weight part.

Moreover, it is preferable to contain less than 30 weight% of compounds of the molecular weight 500 or less which have two or more oxetanyl groups in 1 molecule as (E) component.

Moreover, it is preferable that at least one of plastic films is a cellulose film or (meth) acrylic-type resin.

Moreover, this invention is a laminated body which consists of a base material, the hardened | cured material of the above-mentioned active-energy-ray-curable adhesive composition for plastic films, and another base material,

It relates to a laminate in which both or one side of the substrate and the other substrate are plastic films.

As plastic films, it is preferable that at least one is a cellulose film or (meth) acrylic-type resin.

Moreover, this invention is a manufacturing method of the laminated body which coats the said composition to a base material, attaches another base material to a coating surface, and irradiates an active energy ray from either side of the said base material or the said other base material,

The manufacturing method of the laminated body whose both or one side of the said base material and the said other base material is plastic films.

ADVANTAGE OF THE INVENTION According to this invention, the active energy ray hardening-type adhesive composition which is excellent also in sclerosis | hardenability, is excellent in the adhesive force to various plastic films containing a cellulose film and a (meth) acrylic-type resin, and is excellent also in colorless transparency. For this reason, it can use suitably for manufacture of various optical films used for a liquid crystal display, an organic electroluminescent display, etc. Moreover, also for uses other than a display, it can use suitably also for the various uses which require sclerosis | hardenability, adhesive force, and transparency also, for example in a window, a building material, etc.

The present invention,

(A) component: The aromatic epoxy compound whose weight average molecular weight is 500 or more

(B) component: Polyglycidyl ether of the polyol which has C2-C10

(C) component: the compound which has alicyclic epoxy group

(D) component: Photocationic polymerization initiator

As a composition containing

The content rate of the said (A)-(D) component is the whole composition,

(A) Component: 1-30 wt%

(B) Component: 20-70 wt%

(C) component: 10-60 wt%

(D) component: 0.5-10% by weight

The present invention relates to an active energy ray-curable adhesive composition for films made of phosphorus plastic.

Hereinafter, the preferable use method of (A)-(D) component, another component, and the composition of this invention is demonstrated in detail.

1. (A) Component

(A) A component is an aromatic epoxy compound whose weight average molecular weight (henceforth "Mw") is 500 or more.

In this invention, an aromatic epoxy compound means the epoxy compound which the glycidyl ether group or the glycidyl ester group couple | bonded with the aromatic ring directly, Even if it is a low molecular weight compound, it is a compound also conventionally called "epoxy resin."

Mw of (A) component is 500 or more, It is preferable that it is the range of 500-50,000, It is more preferable that it is the range of 1,000-20,000, It is further more preferable that it is the range of 1,000-10,000, It is the range of 2,000-10,000 Particularly preferred.

When Mw is less than 500, the adhesive force with plastic films, especially (meth) acrylic-type resin becomes low. Further, for this same reason, Mw is preferably 50,000 or less.

In the present invention, Mw means Mw in terms of polystyrene measured by gel permeation chromatography (GPC).

As (A) component, a solid aromatic epoxy compound is preferable at 25 degreeC, and the aromatic epoxy compound whose softening point is 40 degreeC or more is specifically, preferable. By using the aromatic epoxy compound whose softening point is 40 degreeC or more, adhesive force with plastic films, especially (meth) acrylic-type resin can be improved further. The softening point is more preferably 50 ° C or more and 200 ° C or less, still more preferably 60 ° C or more and 170 ° C or less, particularly preferably 70 ° C or more and 140 ° C or less.

In this invention, a softening point means the measured value measured by the ring and ball method of JISK7234.

It is preferable that the number of the epoxy groups contained in 1 molecule of (A) component is 2 or more from the point which can improve the adhesive force with plastic films further. Moreover, glycidyl ether group is more preferable than glycidyl ester group for the same reason.

As a preferable specific example of (A) component, bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol A-type epoxy resin, bisphenol A, bisphenol F, and epichlorohydrin polycondensed, phenol novolak-type epoxy resin, cresol whose Mw is 500 or more Novolak-type epoxy resin, bisphenol A novolak-type epoxy resin, bisphenol F novolak-type epoxy resin, etc. are mentioned.

As (A) component, since the hardened | cured material of the composition obtained is further excellent in adhesive strength, and further excellent in colorless transparency, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A, bisphenol F, and epichlorohydrin This polycondensed epoxy resin is more preferable, a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are further more preferable, and a bisphenol A type epoxy resin is especially preferable.

As (A) component, you may use said compound individually, or may use 2 or more types.

The content rate of (A) component is 1-30 weight% in the whole composition. When (A) component is less than 1 weight%, the adhesive force of a composition will fall. Moreover, when the content rate of (A) component exceeds 30 weight%, the viscosity of a composition will become high too much and coatability will worsen.

The preferable content rate of (A) component is 3-20 weight% in the whole composition, More preferably, it is 5-15 weight%.

Moreover, since the content rate of (A) component is further excellent in the adhesive force with respect to plastic films, it is preferable that it is less than 100 weight part, and it is more preferable that it is less than 50 weight part with 100 weight part of (B) component mentioned later. .

2. (B) Component

(B) component is polyglycidyl ether of the polyol which has C2-C10.

In addition, "carbon number" in the polyol having 2 to 10 carbon atoms means the number of carbons constituting the site excluding the hydroxyl group in the polyol.

As (B) component, the polyglycidyl ether of an alkane polyol, the polyglycidyl ether of a cycloalkane polyol, the polyglycidyl ether of polyalkylene glycol, the polyglycidyl ether of an aromatic polyol, etc. are mentioned.

The component (B) is preferably a diglycidyl ether of a diol having 2 to 6 carbon atoms, and more preferably a diglycidyl ether of an alkanediol having 4 to 6 carbon atoms.

As a specific example of (B) component, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1, 4- butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6- hexanediol Diglycidyl ether, cyclohexanedimethylol diglycidyl ether, 1, 9-nonanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, dipropylene glycol digly Cylyl ether, tripropylene glycol diglycidyl ether, hydroquinone diglycidyl ether, resorcinin diglycidyl ether, trimethylol propane diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol polyglycidyl ether Dimethyl ether, dipentaerythritol polyglycidyl ether, and the like.

As (B) component, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1, 4- butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6- hexanediol diglycile Of diols having 2 to 6 carbon atoms, exemplified by cylyl ether, hydroquinone diglycidyl ether, resorcin diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, and the like. Diglycidyl ether is more preferable.

As (B) component, the alkane which has 4-6 carbons illustrated by 1, 4- butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, etc. The composition obtained by the diglycidyl ether of diol becomes low viscosity, and it is especially preferable at the point which hardened | cured material is further excellent in adhesive force, and further excellent in colorless transparency.

As (B) component, you may use said compound individually, or may use 2 or more types.

The content rate of (B) component is 20 to 70 weight% in the whole composition. When (B) component is less than 20 weight%, the adhesive force of a composition will fall with respect to most plastic films. Moreover, when the content rate of (B) component exceeds 70 weight%, sclerosis | hardenability of a composition will deteriorate and adhesive force will also deteriorate.

The preferable content rate of (B) component is 30 to 60 weight% in the whole composition, More preferably, it is 35 to 50 weight%.

3. (C) component

(C) component is a compound which has an alicyclic epoxy group. As (C) component, the compound which has two or more alicyclic epoxy groups in 1 molecule is preferable.

Specific examples of the component (C) include 3 ', 4'-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, bis (3, 4-epoxycyclohexylmethyl) adipate, 3 and 4-epoxycyclo Caprolactone modified product of hexylmethyl-3,4-epoxycyclohexanecarboxylate, esterified or caprolactone modified product of polyhydric carboxylic acid and 3,4-epoxycyclohexylmethyl alcohol, dicyclopentadiene dioxide, limonene dioxide Can be mentioned.

As (C) component, the compound shown by following formula (1) is especially preferable.

As (C) component, said compound may be used independently or 2 or more types may be used.

The content rate of (C) component is 10 to 60 weight% in the whole composition. When (C) component is less than 10 weight%, sclerosis | hardenability of a composition will deteriorate and adhesive force will also deteriorate. Moreover, when the content rate of (C) component exceeds 60 weight%, adhesive force falls with respect to plastic films, such as (meth) acrylic-type resin.

The preferable content rate of (C) component is 20-50 weight% in the whole composition, More preferably, it is 25-40 weight%.

Moreover, since the content rate of (C) component is further excellent in the adhesive force with respect to plastic films, it is preferable that (B) component is 100 weight part, and it is less than 100 weight part.

4. (D) component

(D) component is a photocationic polymerization initiator. That is, it is a compound which generate | occur | produces cation or Lewis acid by irradiation of active energy rays, such as an ultraviolet-ray or an electron beam, and starts superposition | polymerization of cationic curable components, such as an epoxy compound and an oxetane compound.

As a specific example of (D) component, a sulfonium salt type | system | group photocationic polymerization initiator, an iodonium salt type | system | group photocationic polymerization initiator, a diazonium salt type | system | group photocationic polymerization initiator, etc. are mentioned.

As an example of a sulfonium salt type photocationic polymerization initiator, for example,

Triphenylsulfonium hexafluorophosphate,

Triphenylsulfonium hexafluoroantimonate,

Triphenylsulfonium tetrakis (pentafluorophenyl) borate,

Diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate,

Diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate,

4, 4'-bis [diphenylsulfonio] diphenylsulfide bishexafluorophosphate,

4, 4'-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenylsulfide bishexafluoroantimonate,

4, 4'-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenylsulfide bishexafluorophosphate,

7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate,

7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthonetetrakis (pentafluorophenyl) borate,

4-phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide hexafluorophosphate,

4- (p-tert-butylphenylcarbonyl) -4'-diphenylsulfonio-diphenylsulfide hexafluoroantimonate,

Triarylsulfonium salts such as 4- (p-tert-butylphenylcarbonyl) -4'-di (p-toluyl) sulfonio-diphenylsulfide tetrakis (pentafluorophenyl) borate .

As an example of an iodonium salt type photocationic polymerization initiator, it is, for example,

Diphenyl iodonium tetrakis (pentafluorophenyl) borate,

Diphenyl iodonium hexafluorophosphate,

Diphenyl iodonium hexafluoroantimonate,

Di (4-t-butylphenyl) iodonium hexafluorophosphate,

Di (4-t-butylphenyl) iodonium hexafluoroantimonate,

Tolyl cumyl iodonium tetrakis (pentafluorophenyl) borate,

(4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate,

Di (4-nonylphenyl) iodonium hexafluorophosphate,

Di (4-alkylphenyl) iodonium hexafluorophosphate

Diaryl iodonium salts, such as these, are mentioned.

As an example of a diazonium salt type photocationic polymerization initiator, it is, for example,

Benzenediazonium hexafluoroantimonate,

Benzenediazonium hexafluorophosphate

Etc. can be mentioned.

(D) component is marketed, and Adeka optomer SP-100, SP-150, SP-152, SP-170, SP-172 [made by ADEKA Corporation], photoinitiator 2074 (made by Rhodia Corporation), Kaya rad PCI-220, PCI-620 [product made by Nippon Kayaku Co., Ltd.], Irgacure 250 (product made in Chiba Japan Corporation), CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI-210S [San Afro Corporation], WPI-113, WPI-116 [manufactured by Wako Junyaku Co., Ltd.], BBI-102, BBI-103, TPS-102, TPS-103, DTS-102, DTS-103 [Midori Chemical Co., Ltd.] etc. are mentioned.

Among these, a sulfonium salt type | system | group photocationic polymerization initiator is preferable and triarylsulfonium salt is more preferable from the reason which is more excellent in active energy ray hardenability, and further excellent in colorless transparency. As the triarylsulfonium salt, triphenylsulfonium hexafluorophosphate and diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate are preferable among the above.

As (D) component, said compound may be used independently, or 2 or more types may be used.

The content rate of (D) component is 0.5 to 10 weight% in the whole composition, Preferably it is 1 to 5 weight%. If the content ratio of (D) component is less than 0.5 weight%, the curability of a composition will deteriorate, and when it exceeds 10 weight%, the adhesive force of a composition will fall or the hardened | cured material of a composition will yellow.

5. Other Ingredients

Although the composition of this invention makes said (A)-(D) component essential, various components (henceforth "other component") can be mix | blended according to the objective.

As other components, cation-curable compounds (henceforth "other cation-curable component") other than said (A) component, (B) component, and (C) component, water, a radical curable component, various additives Can be mentioned.

5-1. Other Cation Curable Ingredients

As another cation curable component, the compound which has an epoxy group other than (A) component, (B) component, and (C) component, the compound which has an oxetanyl group, the compound which has a vinyl ether group, etc. are mentioned.

In the case of containing other cationic curable components, the total of these content ratios is preferably less than 30% by weight, more preferably less than 20% by weight, still more preferably less than 10% by weight in the whole composition. Do.

As a specific example of compounds which have epoxy groups other than (A) component, (B) component, and (C) component, the diglycidyl ether of bisphenol A (less than Mw 500) and the diglycidyl ether of bisphenol F (less than Mw 500) ), Diglycidyl ether of brominated bisphenol A (less than Mw 500), phenol novolac type epoxy resin (less than Mw 500), cresol novolac type epoxy resin (less than Mw 500), biphenyl type epoxy resin (less than Mw 500) ), Aromatic epoxy resins less than Mw 500 such as terephthalic acid diglycidyl ester and phthalic acid diglycidyl ester; And

Polyethylene glycol (6 or more repeats) diglycidyl ether, polypropylene glycol (4 or more repeats) diglycidyl ether, polytetramethylene glycol (3 or more repeats) diglycidyl ether, hydrogenated bisphenol A di Diglycidyl ether of C11 or more diols, such as glycidyl ether and polybutadiene diglycidyl ether of both terminal hydroxyl groups, etc. are mentioned.

In addition to these, epoxidized vegetable oil, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, internal epoxide of polybutadiene, and double bonds of styrene-butadiene copolymer are partially epoxidized compounds. [For example, "epofland" manufactured by Daicel Chemical Industry Co., Ltd.) and a compound in which isoprene units of block copolymers of ethylene-butylene copolymers and polyisoprene are partially epoxidized (for example, manufactured by KRATON Co., Ltd.). "L-207"), etc. are mentioned.

As the compound having an oxetanyl group, a compound having a molecular weight of 500 or less (hereinafter referred to as "(E) component") having two or more oxetanyl groups in one molecule is preferable.

Specific examples of the component (E) include bis [(3-ethyloxetan-3-yl) methyl] ether, bis [(3-methyloxetan-3-yl) methyl] ether and bis [(oxetane-3- Yl) methyl] ether, 1,4-bis [(3-ethyloxetan-3-yl) methoxy] methyl] benzene, 1,4-bis [(3-ethyloxetan-3-yl) methoxy] Benzene, 1, 3-bis [(3-ethyloxetan-3-yl) methoxy] benzene, 1, 2-bis [(3-ethyloxetan-3-yl) methoxy] benzene, 4, 4 ' -Bis [(3-ethyloxetan-3-yl) methoxy] biphenyl, 2,2'-bis [(3-ethyloxetan-3-yl) methoxy] biphenyl, 1, 1, 1- Tris [(3-ethyloxetan-3-yl) methoxymethyl] propane, 1, 2-bis [(3-ethyloxetan-3-yl) methoxy] ethane, 1, 2-bis [(3- Ethyloxetan-3-yl) methoxy] propane, 1, 4-bis [(3-ethyloxetan-3-yl) methoxy] butane and 1, 6-bis [(3-ethyloxetane-3- I) methoxy] hexane etc. are mentioned.

As (E) component, bis [(3-ethyloxetan-3-yl) methyl] ether is preferable.

Specific examples of oxetane compounds other than the component (E) include alkoxyalkyl group-containing monofunctional oxetane and 3-ethyl-3-phenoxymethyl jade, such as 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane. Aromatic group containing monofunctional oxetane, such as cetane, the etherification modified | modified by 3-chloromethyl-3-ethyl oxetane of the 3-ethyl-3-hydroxymethyl oxetane, the novolak-type phenol- formaldehyde resin, 3 -[(3-ethyloxetan-3-yl) methoxy] propyltrimethoxysilane, 3-[(3-ethyloxetan-3-yl) methoxy] propyltriethoxysilane, 3-[(3 And hydrolysis condensates of -ethyloxetan-3-yl) methoxy] propyltrialkoxysilane, and condensation reaction products of 3-ethyloxetan-3-ylmethanol and silanetetraol polycondensates.

As a specific example of a vinyl ether compound, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol divinyl ether, cyclohexane dimethanol Divinyl ether and the like.

5-2. water

The composition of the present invention may intentionally add an appropriate amount of water to the whole composition. The presence or absence of addition of water may be optimized according to the type of films. As for content of water, less than 3 weight% is preferable in the whole composition.

5-3. Radical curable components

The composition of this invention may contain a radical curable component. When it contains a radical curable component, it is preferable that they are 120 weight part or less with respect to 100 weight part of total amounts of a cation curable component, It is more preferable that it is 100 weight part or less, It is further more preferable that it is 50 weight part or less.

As a radical curable component, a (meth) acryloyl group containing compound etc. are mentioned. Moreover, as those molecular weight, various things can be selected and any of a monomer, an oligomer, and a polymer may be sufficient.

As the (meth) acryloyl group-containing compound, a compound having one (meth) acryloyl group in the molecule [hereinafter referred to as "monofunctional (meth) acrylate") and two or more (meth) acryloyl groups in the molecule The compound which has a following (it calls "a polyfunctional (meth) acrylate" hereafter) is mentioned.

As a specific example of monofunctional (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl ( Meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxy Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 1, 4- Cyclohexanedimethylol mono (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenol Alkylene oxide part (Meth) acrylate of water, (meth) acrylate of p-cumylphenolalkylene oxide adduct, (meth) acrylate of ο-phenylphenolalkylene oxide adduct, (meth) acrylate of nonylphenolalkylene oxide adduct, 2-methoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, (meth) acrylate of alkylene oxide adducts of 2-ethylhexyl alcohol, pentanediol mono (meth) acrylate, hexanediol Mono (meth) acrylate, mono (meth) acrylate of diethylene glycol, mono (meth) acrylate of triethylene glycol, mono (meth) acrylate of tetraethylene glycol, mono (meth) acrylate of polyethylene glycol, Mono (meth) acrylate of dipropylene glycol, Mono (meth) acrylate of tripropylene glycol, Mono (meth) acrylate of polypropylene glycol, 2-hydroxy- 3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, (2-ethyl-2-methyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, (2-isobutyl-2-methyl-1, 3-dioxolan-4-yl) methyl ( Meta) acrylate, (1,4-dioxaspiro [4,5] decan-2-yl) methyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth ) Acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, 2- (meth) acryloyloxyethyl isocyanate, allyl (meth) acrylate, N- (meth) acryloyloxy Ethylhexahydrophthalimide, N- (meth) acryloyloxyethyltetrahydrophthalimide, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl succinic acid, ω- Leboxy-polycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyl Oxypropyldimethoxymethylsilane, 3- (meth) acryloyloxypropyltriethoxysilane, etc. are mentioned.

In the alkylene oxide adduct, ethylene oxide, propylene oxide, etc. may be mentioned as the alkylene oxide.

Specific examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. , 1, 6-hexanediol di (meth) acrylate, 3-methyl-1, 5-pentanedioldi (meth) acrylate, 2-butyl-2-ethyl-1, 3-propanedioldi (meth) acrylic Di (meth) acrylates of aliphatic diols such as late and 1,9-nonanediol di (meth) acrylate;

Di (meth) acrylates of alicyclic diols such as cyclohexanedimethylol di (meth) acrylate and tricyclodecanedimethylol di (meth) acrylate;

Alkylene glycol di (meth) acrylates, such as diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate ;

Esterification products of neopentyl glycol, hydroxypivalic acid and (meth) acrylic acid;

Di (meth) acrylate of alkylene oxide adducts of bisphenol-based compounds such as di (meth) acrylate of bisphenol A alkylene oxide adduct;

Di (meth) acrylates of hydrogenated bisphenol compounds such as di (meth) acrylate of hydrogenated bisphenol A;

Polyol poly (meth), such as trimethylol propane tri (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate, dipentaerythritol penta or hexa (meth) acrylate Acrylates;

Tri (meth) acrylate of trimethylolpropanealkylene oxide adduct, tetra (meth) acrylate of ditrimethylolpropanealkylene oxide adduct, tri or tetra (meth) acrylate, dipentaerythritol of pentaerythritol alkylene oxide adduct Poly (meth) acrylates of polyolalkylene oxide adducts such as penta or hexa (meth) acrylate of alkylene oxide adducts;

Urethane (meth) acrylates;

Epoxy (meth) acrylates; And

Polyester (meth) acrylate etc. are mentioned.

The polyester (meth) acrylate may be a dendrimer type (meth) acrylate.

In the alkylene oxide adduct, ethylene oxide, propylene oxide, etc. may be mentioned as the alkylene oxide.

When the composition of this invention contains a radical curable component, it is preferable to contain 0.1-10 weight% of radical photopolymerization initiators based on the whole composition. As an optical radical polymerization initiator, what is generally available can be used.

5-4. Various additives

In addition to these, the composition of this invention may contain various additives other than a curable component, unless the effect of this invention is impaired. As various additives, thermal cationic polymerization initiator, photosensitizer, ultraviolet absorber, light stabilizer, antioxidant, polymerization inhibitor, silane coupling agent, polyol compound, polymer, tackifier, filler, metal fine particles, metal oxide fine particles, ions A trapping agent, an antifoamer, a leveling agent, a pigment, a pigment, etc. are mentioned.

Examples of the polymer include poly (meth) acrylic acid ester, polyvinyl acetate, polystyrene, polyether, polyester and the like.

As a polymer, what contains cationic polymerizable groups, such as an epoxy group, an oxetanyl group, and a vinyl ether group, can be used in a molecule | numerator. Moreover, the thing containing radically polymerizable groups, such as a (meth) acryloyl group and a vinyl group, can be used in a molecule | numerator.

6. Active Energy Ray Curable Adhesive Compositions for Plastic Films

This invention relates to the active energy ray hardening-type adhesive composition for plastic films containing said (A)-(D) component as an essential component.

It is preferable that the composition of this invention is 0.1 weight% or less in total chlorine content in a composition. As a method of reducing the total chlorine content in a composition, the method of using distillation refinement as a (B) component, etc. are mentioned, for example.

As a manufacturing method of the composition of this invention, it is good according to a conventional method, it can manufacture by mixing the said (A)-(D) component as needed, adding another component, and stirring according to a conventional method. In this case, it can heat or heat as needed.

What is necessary is just to set suitably as a viscosity of the composition of this invention according to an intended purpose.

In order to obtain the coating property which can be used in the manufacturing process of the laminated body using plastic films, ie, the coating surface excellent in smoothness also in a thin film, it is preferable that the viscosity in 25 degreeC is 1,000 mPa * s or less, and it is more preferable that it is 10-500 mPa * s. It is preferable and it is especially preferable that it is 20-100 mPa * s or less.

In this invention, the viscosity of a composition means the value measured at 25 degreeC using the E-type viscosity meter.

The composition of the present invention can be used for adhesion between plastic films, adhesion between plastic films and various other substrates (hereinafter referred to as "other substrate"). That is, it can be used for bonding two substrates at least one of which is plastic films. In addition, in the following, when it only says "substrate", it means the general term of plastic films and other base materials. As another base material, glass, a metal oxide, a metal, a tree, paper, etc. are mentioned.

As a material in plastic films, for example, a cellulose film, (meth) acrylic resin, cycloolefin polymer, polystyrene, acrylic / styrene copolymer, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, ABS resin And polyamides, polyesters, polycarbonates, polyurethanes, and chlorinated polypropylenes. Examples of the cellulose-based film include triacetyl cellulose, cellulose acetate butyrate, and the like. Examples of the (meth) acrylic resins include polymethyl methacrylate, copolymers containing methyl methacrylate as a main component, and copolymers containing no methyl methacrylate as polymerized monomers.

The composition of this invention can be preferably applied to a cellulose film and (meth) acrylic-type resin among these plastic films.

Examples of the metal oxides include tin oxide, indium oxide, titanium oxide, and zinc oxide. As a metal, gold, silver, copper, aluminum, iron, nickel, titanium, etc. are mentioned, for example. Among these, when the transparent thin film formed by vapor deposition, sputtering, etc. is a base material, since transparency which is one of the characteristics of the composition of this invention is often desired, it is applied more preferably.

In addition, when plastic films are hard adhesive materials, an activation process can be given to one or both surfaces before coating the composition of this invention. Examples of the surface activation treatment include plasma treatment, corona discharge treatment, chemical solution treatment, roughening treatment and etching treatment, and flame treatment. These may be used in combination.

7. How to use

As a usage method of the composition of this invention, it is good according to a conventional method, and after coating a composition to a base material, it adhere | attaches with another base material, the method of irradiating an active energy ray, etc. are mentioned.

The composition of this invention is suitable for the case where a thin-layer adherend is adhere | attached as a base material. The use method in the case of adhering a thin layer to-be-adhered body is good according to the method currently performed by manufacture of a laminate. For example, the method of coating a composition on a 1st thin layer adherend, attaching a 2nd thin layer adherend to this, and irradiating an active energy ray, etc. are mentioned.

Coating on the substrate may be performed according to a conventionally known method, and natural coater, knife belt coater, floating knife, knife over roll, knife on blanket, spray, dip, kiss roll, squeeze roll, reverse roll, air blade, curtain flow coater , Comma coater, gravure coater, micro gravure coater, die coater and curtain coater.

Moreover, what is necessary is just to select the coating thickness of the composition of this invention according to the base material to be used, and a use, Preferably it is 0.1-10 micrometers, More preferably, it is 1-5 micrometers.

Examples of the active energy rays include visible rays, ultraviolet rays, X-rays, and electron beams, but ultraviolet rays are preferable because inexpensive devices can be used.

As a light source in the case of hardening by an ultraviolet-ray, various things can be used, For example, a pressurized or high pressure mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, a carbon arc lamp, LED, etc. are mentioned. Among these, a high pressure mercury lamp and a metal halide lamp are especially preferable. The irradiation amount of ultraviolet rays is preferably 10 to 1,000 mJ / cm 2 in the UV-B region (near 310 nm), more preferably 20 to 500 mJ / cm 2, still more preferably 50 to 200 mJ / cm 2.

When hardening with an electron beam, various apparatuses can be used as an EB irradiation apparatus which can be used, For example, a cockcroft-walton type | mold, a van degraf type | mold, a resonance transformer type apparatus, etc. are mentioned.

As absorbed dose of an electron beam, 1-200 kGy is preferable, More preferably, it is 10-100 kGy.

As an acceleration voltage of an electron beam, what is necessary is just to set suitably in the range of 80-300 kV according to the film thickness of films, and 200 kV is preferable when the film thickness of films is 100 micrometers.

As oxygen concentration of an electron beam irradiation atmosphere, 500 ppm or less is preferable, More preferably, it is 300 ppm or less.

8. Laminated body and its manufacturing method

The composition of this invention can be used suitably for manufacture of a laminated body.

As a structure of a laminated body, a laminated body comprised from a base material, the hardened | cured material of the said composition, and another base material, Comprising: Both or one of the said base material and the other base material is plastic films.

As plastic films, it is preferable that at least one is a cellulose film or (meth) acrylic-type resin.

As a manufacturing method of a laminated body, the method of coating the above-mentioned composition on a base material, attaching another base material to the said coating surface, and irradiating an active energy ray from either side of the said base material or the said other base material, etc. Can be mentioned.

In this case, plastic films are used as the substrates of both the substrate and the other substrate, or at least one substrate. Specific examples and preferred examples of the substrate are as described above.

Examples of the use of the obtained laminate include various optical films used in liquid crystal displays, organic EL displays, and the like. Specifically, hard coat films imparting functionality such as anti-fingerprint and non-glossiness, front panels of touch panels, and flat plates , Retardation film, viewing angle compensation film, brightness enhancement film, antireflection film, anti-glare film, lens sheet, and diffusion sheet.

(Example)

An Example and a comparative example are given to the following, and this invention is demonstrated more concretely. However, the present invention is not limited by these examples.

In addition, below, "part" means a weight part and the numerical value which shows the mixture ratio in a table means a weight%.

In an Example and a comparative example, each component used for preparation of a composition is as follows, and the symbol in Table 1 means the following compound.

(A) ingredient

J-1004: Bisphenol A solid epoxy resin (Mw: 4,500, softening point 97 ° C), "jER-1004" manufactured by Mitsubishi Chemical Corporation

(B) ingredient

BD-DGE: 1, 4-butanediol diglycidyl ether (distilled and refined product), "SR-14BJ" made by Sakamoto Pharmaceutical Co., Ltd.

(C) component

C-2021: 3 ', 4'-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, "Celoxide 2021P" manufactured by Daicel Co., Ltd.

(D) component

110P: triarylsulfonium hexafluorophosphate (active ingredient 100%), "CPI-110P" manufactured by San Apro Co., Ltd.

(E) component

OXT-221: Bis [(3-ethyloxetane-3-yl) methyl] ether, "Aron oxetane (registered trademark) OXT-221" manufactured by Toa Synthetic Co., Ltd.

(A) '[Aromatic epoxy resins other than (A) component]

J-828: Bisphenol A liquid epoxy resin (Mw: 370), manufactured by Mitsubishi Chemical Corporation "jER-828"

1. Examples 1-2, Comparative Examples 1-2

1) Preparation of Active Energy Ray Curing Composition

Each component shown in Table 1 was mix | blended in each ratio, and it stirred and mixed according to the conventional method, and prepared the active energy ray hardening-type adhesive composition.

2) Preparation of Laminate

The corona treatment was performed on the cellulose film (henceforth "CEL") of 80 micrometers in thickness, and the methacryl-type resin (henceforth "PMMA") of 75 micrometers in thickness as an easily bonding process.

Next, after coating the adhesive composition obtained by 1.1) to the corona treatment surface of PMMA with 3 micrometers thickness by the bar coater, CEL was laminated. At this time, it arrange | positioned so that the corona treatment surface of CEL might be in contact with a coating surface.

Finally, measurement of accumulated light quantity 100mJ / cm2 (UV-B, UV POWER PUCK made by Heraeus Co., Ltd.) from the surface of PMMA by ultraviolet ray irradiation device (use of metal halide lamp) with belt conveyor made by iGraphics Co., Ltd. Value) was irradiated with ultraviolet rays to cure the adhesive composition, and the curing rate was evaluated according to the following method.

After the obtained laminated body was left to stand on condition of 23 degreeC and 50% of a relative humidity for 1 day, colorless transparency and adhesive force were evaluated by the following method.

2. Evaluation method

1) Evaluation of Curing Rate

The film was peeled off immediately after being irradiated with ultraviolet rays in 1.2) and discharged from the conveyor, and evaluated based on the following criteria.

A: It was not an adhesive state but cured.

B: It was an adhesive state.

C: It was a liquid phase.

2) Evaluation of Adhesion

1. The laminated body obtained by 1.2) was cut out to 1 inch in width and 10 cm in length, and the T peeling test (peel rate: 300 mm / min) was performed, and it evaluated based on the following criteria.

A: There existed adhesive force so that a film might be torn.

B: The film was not torn, but 3N / inch or more was adhesive force.

C: adhesion of 1 N / inch or more and less than 3 N / inch.

D: It was a weak strength of less than 1 N / inch.

3) Evaluation of colorless transparency

The laminated body obtained by 1.2 was laminated | stacked 5 visually, and it evaluated based on the following criteria.

A: No opacity or yellowing was felt.

B: Some opacity or yellowing was felt.

C: Opacity or yellowing was clearly felt.

Example
One Example
2 Comparative example
One Comparative example
2 (A) J-1004 12 12 12 (A) ' J-828 12 (B) BD-DGE 40 40 40 40 (C) C-2021 45 32 45 (D) 110P 3 3 3 3 (E) OXT-221 13 45 Evaluation results Curing rate A A B A Adhesion B A D C Colorless transparency A A A A

The composition of Examples 1-2 of this invention was all favorable for a cure rate, adhesive force, and colorless transparency. Example 2 which contains less than 30 mass% of (E) component in the whole composition, and whose content of (C) component is smaller than (B) component has the outstanding adhesive force to both films of PMMA and CEL, and a film is torn. It was about.

On the other hand, the composition of Comparative Example 1 in which the component (A) was replaced with a bisphenol A liquid epoxy resin not applicable to the component (A) had insufficient curing rate and very low adhesive force. The comparative example 2 which does not contain the (C) component had low adhesive force with CEL.

Industrial availability

The composition of the present invention can be used as an adhesive for plastic films, and in particular, can be suitably used for adhesion of optical films used for liquid crystal displays, organic EL displays and the like.

Claims (13)

(A) component: The aromatic epoxy compound whose weight average molecular weight is 500 or more
(B) component: Polyglycidyl ether of the polyol which has C2-C10
(C) component: the compound which has alicyclic epoxy group
(D) component: Photocationic polymerization initiator
As a composition containing
The content rate of the said (A)-(D) component is the whole composition,
(A) Component: 1-30 wt%
(B) Component: 20-70 wt%
(C) component: 10-60 wt%
(D) component: 0.5-10 weight%
Active energy ray hardening-type adhesive composition for plastic films or sheets.
The method of claim 1,
(A) A component is a weight average molecular weight 1,000-20,000, and the number of the epoxy groups contained in 1 molecule is a compound of 2 or more
Active energy ray hardening-type adhesive composition for plastic films or sheets.
The method according to claim 1 or 2,
(A) component is bisphenol-A epoxy resin and / or bisphenol F-type epoxy resin
Active energy ray hardening-type adhesive composition for plastic films or sheets.
The method according to any one of claims 1 to 3,
(B) Component is diglycidyl ether of diol which has C2-C6
Active energy ray hardening-type adhesive composition for plastic films or sheets.
The method according to any one of claims 1 to 4,
(B) Component is diglycidyl ether of alkanediol having 4-6 carbon atoms
Active energy ray hardening-type adhesive composition for plastic films or sheets.
The method according to any one of claims 1 to 5,
(C) component is a compound shown by following formula (1)
Active energy ray hardening-type adhesive composition for plastic films or sheets.

The method according to any one of claims 1 to 6,
(D) component is a sulfonium salt type | system | group photocationic polymerization initiator
Active energy ray hardening-type adhesive composition for plastic films or sheets.
The method according to any one of claims 1 to 7,
3-20 weight% of (A) component, 30-60 weight% of (B) component, 20-50 weight% of (C) component, and 1-5 weight% of (D) component in the whole composition,
(B) Component is 100 weight part, content of (A) component is less than 100 weight part, and content of (C) component is less than 100 weight part
Active energy ray hardening-type adhesive composition for plastic films or sheets.
The method according to any one of claims 1 to 8,
As the component (E), further comprising less than 30% by weight of a compound having a molecular weight of 500 or less having two or more oxetanyl groups in one molecule in the whole composition
Active energy ray hardening-type adhesive composition for plastic films or sheets.
The method according to any one of claims 1 to 9,
At least one of the plastic film or sheet is a cellulose film or (meth) acrylic resin
Active energy ray hardening-type adhesive composition for plastic films or sheets.
As a laminated body which consists of a base material, the hardened | cured material of the active-energy-ray-curable adhesive composition for plastic films or sheets of any one of Claims 1-10, and another base material,
Both or one side of the said base material and the said other base material is a plastic film or sheet
Laminate.
The method of claim 11,
At least one of the plastic film or sheet is a cellulose film or (meth) acrylic resin
Laminate.
The laminated body which coats the composition as described in any one of Claims 1-10 to a base material, adheres another base material to a coating surface, and irradiates an active energy ray from either side of the said base material or the said other base material. As a manufacturing method of
Both or one side of the said base material and the said other base material is a plastic film or sheet
The manufacturing method of a laminated body.