TWI359180B - Pressure-sensitive adhesive composition and adhesi - Google Patents

Description

1359180 The present invention comprises the following inventions: (1) A pressure-sensitive adhesive composition comprising (1) a copolymer (A) obtained by copolymerization of a (meth) acrylate and a hydroxy group-containing monomer, and (ii) (Methyl) • Acrylic acid is a copolymer (B) obtained by copolymerization of at least one isocyanate group in its molecule. (2) The pressure-sensitive adhesive composition according to (1) above, wherein the copolymer (a) has a weight average molecular weight of between 500,000 and 2, 〇〇〇, 000 (based on polyphenylethylene and determined by GPC). (3) The pressure-sensitive adhesive composition according to (1) or (2) above, wherein the copolymer has a weight average molecular weight of 5 Å, between 〇〇〇 and ijooooo (determined by polystyrene and determined by GPC). (4) The pressure-sensitive adhesive composition according to any one of (1) above, which contains from 0.1 to 3 parts by weight of the copolymer (B) per part by weight of the copolymer (A). (5) The pressure-sensitive adhesive composition according to any one of the above (1) to (4), which is used for an optical element. (6) A pressure-sensitive adhesive sheet comprising a layer of the pressure-sensitive adhesive composition according to any one of the above (1) to (5), which is provided on at least one side of the substrate sheet. (7) An adhesive optical element comprising a layer of the pressure-sensitive adhesive composition according to any one of the above (1) to (5), which is provided on at least one side of the sheet-like optical element. (8) The adhesive optical element according to (7) above, wherein the sheet-like optical element is a polarizing plate or a phase difference plate. The pressure-sensitive adhesive composition of the present invention is characterized in that the copolymer (B) is used as a crosslinking agent. Copolymer (B) is a kind of acrylamide, N-mercaptopropenylamine, N-mercaptopropenylamine, N_ mercaptopropene, similar to 99064.doc 1359180-based acrylamide, which is intended to be used as a pressure-sensitive adhesive. Indoleamine, and N-hydroxydecylmercaptopropenylamine; (meth)acrylic acid monoalkylaminoalkyl esters such as (mercapto)acrylic acid monomethylaminoethyl ester, (meth)propionic acid Monoethylaminoethyl ester, (mercapto)acrylic acid monodecylaminopropyl propyl ester and (mercapto)acrylic acid monoethyl.aminopropyl vinegar; and ethylenically unsaturated acid such as acrylic acid, hydrazine Acrylic acid, maleic acid, isaconic acid and thiconic acid. These monomers may be used singly or in combination of two or more types. • The weight ratio of (meth) acrylate to the functional group-containing monomer to be used in the production of the above copolymer (A) is usually between 99.9:0.1 and 80:20, preferably 99:1 and 90:1 〇 between. Regarding the above copolymer (A), in addition to the (meth) acrylate and the functional group-containing monomer, other monomers may be used as necessary. Examples of such "other" monomers which may be used if necessary include: vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene, and isobutylene; and olefins such as ethylene chloride and vinylene. Gas; styrene monomer such as stupid ethylene and cardiomethyl styrene; diene monomer Φ such as butadiene, isoprene and chloroform; nitrile monomers such as acetonitrile and methyl acetonitrile; and N, N-II Alkyl substituted acrylamides such as N,N-dimethyl acrylamide and N,N-dimethyl methacrylamide. These monomers may be used singly or in combination of two or more kinds thereof. The other π monomer is usually used in an amount of usually from 0 to 20 parts by weight, preferably from 0 to 10 parts by weight per 100 parts by weight of the monomer comprising the above copolymer (Α). In the pressure-sensitive adhesive composition, the form of the above copolymer (Α) is not particularly limited and may be in the form of any random copolymer, block copolymer and graft copolymer. Further, regarding the molecular weight, Preferably, the weights have a weight average of 99064.doc 1359180 and the average molecular weight range is 5 GM _ 2

When the average molecular weight is less than 5 〇 (), _, the long-term adhesion will not be ^. When the weight average molecular weight is less than 2,00 Torr, the swelling property and shrinkage property of the substrate below the town may be deteriorated. In view of the adhesion and the durability of the point-to-point J, the swelling and shrinkage of the raw and the following substrates are preferably such that they have a weight average of 3: 800,000 and 1,800,000.罝古舌 e, ~ 成寻 has a weight average molecular weight of 1,7 〇〇, _. Further, the above weight average molecular weight is determined by gel permeation separation (Gpc) according to polystyrene. In the present invention, one type of copolymer (4) may be used, or two or more types thereof may be used in combination. The radical polymerizable monomer having at least one isocyanato group in the molecule thereof for use in the above copolymer (8) is not particularly limited as long as it imparts a function as a crosslinking agent to the copolymer (B) and can be a 1 (tetra) group. Examples of the polymerizable monomer include a (meth)acrylic brewed derivative having at least one cyanic acid anhydride group (for example, 2-isocyanylethyl glycolate (meth)acrylate, or a compound having (iv) or a trans group (such as Mercapto)acrylic acid, (meth)acrylic acid 2_by thiophene or (meth)acrylic acid 4· butyl butyl ester and polyfunctional isocyanate compounds such as toluene diisocyanate or diisocyanate Free radical polymerizable monomer obtained from radical polymerizable monomer of dimethyl ester. These monomers may be used singly or in combination of two or more types thereof. (Mercapto) acrylate is used for the manufacture of the above copolymer. The weight ratio of the radical polymerizable monomer having at least one isocyanate group in its molecule of (B) is usually between 99.9:0.1 and 80:20, preferably between 99:1 and 90:1 Torr. The above copolymer (B) 'except (mercapto) acrylate and having at least one 99064.doc •1 0·1359180 isocyanate groups in addition to the free radical polymerizable monomers in the molecule, if necessary, other monomers may be used. If necessary, other examples of monomers include: ethylene vinegar Such as ethyl acetate vinegar and ethyl vinegar propionate; dilute tobaccos such as ethylene, propylene, and isobutylene; toothed olefins such as ethylene gas, s-ene monomers such as styrene-butene α-mercapto styrene; Dibutyl, isopentadiene and gas flat, nitrile monomers such as acetonitrile and methyl acetonitrile; base substituted acrylamides such as N,N-dimercaptopropenylamine and N,N-dimethylmethyl Acrylamide. These monomers can be used alone in more than 5 types; Group: Use. If necessary, use this "other" monomer usually in the amount of each of the above two copolymers. The monomer of (B) is usually from 〇 to 1 part by weight, preferably from 0 to 5 parts by weight. In the pressure-sensitive adhesive composition of the present invention, the form of the above copolymer (b) is not particularly limited. It may be in the form of any random copolymer, block copolymer and graft copolymer. Further, with respect to molecular weight, it is preferred to have such The weight average molecular weight range is 50,0 〇〇 and 1,200,0 ( (according to polyphenyl φ ethylene and determined by GPC). When the weight average molecular weight is less than 5 〇, 〇〇〇, pressure sensitive adhesion The coagulating power of the agent is not obtained and the durability is deteriorated. When the weight average molecular weight exceeds 2,000,000, the viscosity of the coating solution is remarkably increased and the coating ability is deteriorated. In view of these factors, the weight average molecular weight is preferably 100,000 and 1 Between 〇〇〇, 〇〇〇, particularly preferably a weight average molecular weight of between 150,000 and 9500,000. In the present invention, a copolymer of the type (B), or two or more types thereof may be used. In combination, the compounding ratio of the copolymer (B) to the copolymer (A) is usually from 0.5 to 15 parts by weight per 100 parts by weight of the copolymer (A), preferably from 0.5 to 15 parts by weight of the copolymer (B). ). 99. The polymerization of the above copolymers (A) and (B) is carried out by a conventional polymerization method such as solution polymerization or f-polymerization. The reaction temperature for the polymerization is usually from 5 to 85 C', preferably from 55 to 80. (: t When performing solution polymerization, the single system is in the range of ... and (9) wt%, more than 5 and 50 wt% (solid content), using a polymerization initiator such as azobisisobutyronitrile or peroxidation The throttling is carried out in a solvent such as propylene, benzene, toluene's ethyl acetate, hexanyl, gypsum or isopropanol. The amount of the polymerization initiator to be compounded is usually 0.05 to 1 per 100 parts of the total monomer. The pressure-sensitive adhesive composition of the present invention may be further supplemented with various additives conventionally known for use in a pressure sensitive spotting agent composition, for example, a plasticizer, a Shi Xitong coupling agent, and an ultraviolet absorption. The agent and the antioxidant are as long as the additive does not adversely affect the object of the present invention. The pressure-sensitive adhesive composition of the present invention is suitable for an optical element. The combination of the pressure-sensitive adhesive composition of the present invention for an optical element The material is preferably optically transparent. The adhesive sheet of the present invention comprises a layer (hereinafter abbreviated as "bonding layer,") comprising the above pressure-sensitive adhesive composition, one of which is disposed on the surface of the substrate sheet. Upper substrate sheet Examples include: paper substrates such as cellophane, coated paper, and coated paper, laminated paper comprising a thermoplastic resin such as Polyethylene, laminated on a paper substrate; polyester film such as polyethylene terephthalate, polypair a film of butyl phthalate and ethylene naphthalate; a film of a polyolefin film such as polypropylene and polymethyl pentoxide; a film of a plastic film such as polycarbonate and cellulose acetate; and a laminate comprising the film The substrate sheet is suitable for the application according to the adhesive sheet. The adhesive sheet σ of the present invention is used as a component for transferring the adhesive layer to the adherend or as a component to fix the adhesive layer 99064.doc 12 1359180 to the desired adherend. When the adhesive layer is used in the former application, the substrate sheet is usually coated with a release agent such as an anthrone resin. In this case, the thickness of the substrate sheet is not particularly limited, and is usually between about 20 μm and 15 μm. When the adhesive layer is used for the latter application, the type and thickness of the substrate sheet are appropriately selected depending on the application thereof. In this case, if necessary, a general release agent may be disposed on the adhesive layer. In the case of the adhesive layer, the thickness of the adhesive layer is usually about 5 microns and 150 microns. Preferably, the bonding optical element of the present invention is provided with a layer comprising the pressure-sensitive adhesive composition on at least one side of the sheet-like optical element. Examples of the optical element are not particularly limited and include a polarizing plate, a phase difference plate, an anti-reflection plate, and a film for magnifying the viewing angle. Among them, a polarizing plate is preferable. Examples of the polarizing plate include a polarizing plate for a liquid crystal display, and a light amount for adjusting the light. A polarizing plate for a polarizing plate, a polarizing plate for a device using a polarized light interference, and a polarizing plate for an optical defect detector. Among them, a polarizing plate for a liquid crystal cell of a liquid crystal display is particularly advantageous as an adhesive layer. The present invention is described in detail by limiting the examples and comparative examples of the present invention. Further, the weight average molecular weight of the polymer is determined as follows. (Method for measuring weight average molecular weight) Using 1% by weight of a polymer in a tetrahydrofuran (THF) solution as a sample, HLC_8〇2〇 (manufactured by TOSOH CORPORATION; triple tube, tube) at 40 ° C and 1 ml THF solvent / minute 99064.doc -J3- 1359180 GMHXL, TSKgelGMHxl ^ TSKgelG2OOOHxi ^ / ^ a0a. [Reference Example 1] 99 weight-injury n-butyl acrylate, 1 part by weight of acrylic acid 4-butylidene ester and 0.2 weight of azobisisobutyronitrile as a polymerization initiator were added to 2 parts by weight of ethyl acetate. . The solution is at 60. (: stirring for 17 hours, a solution having an acrylate copolymer having a weight average molecular weight of 1,600,000 was obtained. [Reference Example 2]

99 parts s: part of n-butyl acrylate, 1 part by weight of 2-iodoethyl methacrylate and 0.2 part by weight of azobisisobutyronitrile were added as a polymerization initiator to 2 parts by weight of ethyl acetate. The solution was stirred at 6 °t for 17 hours to obtain a solution of an acrylate copolymer having a weight average molecular weight of 850,000. [Reference Example 3]

95 parts by weight of acrylic acid n-butyl ketone, 5 parts by weight of methyl acrylate acid 2 _ acyl acid group" and 0.2 parts by weight of azobisisobutyronitrile as a polymerization initiator added to the weight fraction of acetic acid The solution was stirred at 6 (rc for 17 hours to obtain a solution of an acrylate copolymer having a weight average molecular weight of 920,000. [Reference Example 4] 9 〇 parts by weight of acrylonitrile n-butyl, 1 G by weight methyl Acrylic acid 2-isoinic acid ethyl and 0-2 parts by weight azobisisobutyronitrile were added as a polymerization initiator to the shaking weight of acetic acid. The solution was stirred at 6 Torr for 17 hours to obtain a weight average molecular weight of _, a solution of a copolymer of acrylic acid S. [Reference Example 5] 90 parts by weight of n-butyl acrylate acrylate and 0.5 part by weight of azobis, 10 parts by weight of 2-isocyanoguanidine methacrylate as polymerization initiation The solution was added to 200 99064.doc 14 1359180 parts by weight of acetic acid. The solution was stirred at 6 Torr for 17 hours to obtain a solution having an acrylate copolymer having an average molecular weight of 410 and ruthenium. [Reference Example 6 90 parts by weight of acrylic acid n-butyl, 1 part by weight of methacrylic acid 2 isocyanide Acetic acid ethyl vinegar and G. 2 parts by weight of azobisisobutyronitrile were added as a polymerization initiator to (10) parts by weight of ethyl acetate and 1 part by weight of toluene. The solution was stirred at 6 Torr for 5 hours. A solution of a propylene glycol vinegar copolymer having a weight average molecular weight of 18 M (9) can be obtained.

I. Example 11_0 parts by weight of the copolymer obtained in Reference Example 2 was added to 1 part by weight of the copolymer of the reference compound. The solution was diluted with ethyl acetate to prepare a solution having a concentration of 25%, whereby the binder A was obtained. j

[Example 2J 2. 2 parts by weight of the copolymer obtained in Reference Example 3 was added to (10) parts by weight of the copolymer to be referred to. The solution was diluted with ethyl acetate to prepare a solution having a concentration of 25%, whereby the binder B was obtained. Λ [Example 3] The copolymer obtained in Reference Example 4 was added in an amount of (10) by weight to the copolymer obtained in Reference Example 1. % ^ & diluted with ethyl acetate to prepare a bath having a concentration, whereby a binder 〇 [Example 4] i.00 parts by weight of the copolymer obtained in Reference Example 5 was added to the copolymer obtained in (10) 1.玄> Deficient liquid is diluted with ethyl acetate to prepare a solution having a concentration of gluten solution. Thus, a binder can be obtained. De 99064.doc • 15- 1359180 [Example 5] 1.00 part by weight of the copolymer obtained in Reference Example 6 100 parts by weight of the copolymer obtained in Reference Example 1 was added. The solution was diluted with ethyl acetate to prepare a solution having a concentration of 25%, whereby the binder E was obtained. [Comparative Example 1] 2.50 resetting portion of a trifunctional adduct mainly composed of dinonyl diisocyanate (by

Soken Chemical & Engineering Co., Ltd., manufactured by TD-75, was added to 1 part by weight of the copolymer obtained in Reference Example 1. The solution was diluted with ethyl acetate to prepare a solution having a concentration of 25%, whereby the binder F was obtained. [Comparative Example 2] 50 parts by weight of a trifunctional adduct mainly composed of xylene diisocyanate (by

Soken Chemical & Engineering Co., Ltd. Manufactured: TD-75) was added to 100 parts by weight of the copolymer obtained in Reference Example. The solution was diluted with ethyl acetate to give a concentration of 25. /. The solution 'by this allows a binder 〇 to be obtained. [Comparative Example 3] 0.10 parts by weight of a trifunctional adduct mainly composed of xylene diisocyanate (by

Soken Chemical & Engineering Co., Ltd., manufactured by TD-75, was added to 100 parts by weight of the copolymer obtained in Reference Example 1. The solution was diluted with ethyl acetate to prepare a solution having a concentration of 25%, whereby the binder η was obtained. [Comparative Example 4] 5.7 5 parts by weight of a difunctional adduct mainly composed of isophorone diisocyanate (manufactured by MITSUBISHI CHEMICAL CORPORATION: NY-T-35C) was added to 100 parts by weight of Reference Example 1. Within the copolymer. The solution was diluted with ethyl acetate to prepare a solution having a concentration of 25%, thereby obtaining 99064.doc -16 - 1359180 binder I ^ • anthrone-resin-release-treatment of the polyethylene terephthalate film Face (by lintec

Manufactured by Corporation: SP-PET3811), a transfer member having a thickness of 38 μm and provided with a release layer of an anthrone resin on one side was coated with each of the binders prepared in the above examples and comparative examples using a knife coater. The surface coated with the adhesive was dried at 90 C for 1 minute to form an adhesive layer having a thickness of 25 μm. Subsequently, the bonding layer of the above-mentioned transfer member can be obtained by laminating on a polarizing plate to obtain a polarizing plate having an adhesive layer temporarily attached to the transfer member. The resulting polarizing plates were tested for compatibility, durability, and ability to prevent light leakage. The results are shown in Table 1. 1) Compatibility: The coating/column solution and the dried coating layer were prepared by visual observation after application of the above transfer member. (〇: the appearance has not changed; χ: turbid or white) 2) Durability. The bonding layer of the polarizing plate (size: 233 mm χ 309 mm) with the adhesive from which the transfer element is peeled is attached to the non-inspective glass. . The glass was then subjected to autoclave treatment and then allowed to stand at 8 ° C for 200 hours under dry conditions. The appearance change of the polarizing plate was evaluated visually. (〇: no defect, △: with small bubbles; χ: with bubbles) 3) Ability to prevent light leakage: Adhesive layer of polarizing plate (size: 233 mm χ 309 mm) with transfer agent from which the transfer element is peeled off To non-alkaline glass with a positive Nikons. Then, the glass was subjected to a heat press treatment' and then allowed to stand at 8 ° C for 2 hours under dry conditions. The degree of light leakage was evaluated based on the difference in luminance using MCPD-2(R) (manufactured by 〇tsuka Electronics Co., Ltd.) as follows. 4) Difference in redundancy: Measure the brightness of the center of each end of the polarizing plate from 1 cm 99064.doc 1359180 and the brightness at the center of the polarizing plate, and then obtain the average brightness measured from each end and the brightness at the center. difference. Table 1 Compatibility durability 2) Light leakage prevention ability 3) Coating solution / dried coating layer 80 〇 c drying brightness difference ΔΙ / Μ Example 1: Adhesive A 〇 / 〇 Δ 1.24 Example 2: Adhesive B 〇 /〇〇1.13 Example 3: Adhesive C 〇/〇〇0.85 Example 4: Adhesive D 〇/〇〇1.58 Example 5: Adhesive E 〇/〇〇1.92 Comparative Example 1: Adhesive F. 〇/〇 stripping Non-measurable Comparative Example 2: Adhesive G 〇/〇〇 9.36 Comparative Example 3: Adhesive Η 〇/〇X 1.33 Comparative Example 4: Adhesive I χ/χ 〇 1.20 Effect of the Invention According to the present invention, a pressure can be provided A viscous adhesive composition which can prevent turbidity, bleed and the like from being applied to a coating solution and which has excellent durability and ability to prevent light leakage; and the use of the adhesive sheet and the bonding optical element. 99064.doc 18-

Claims (1)

1359180 Patent application No. 094103068 Chinese application for profit and loss replacement (August 100) X. Patent application: Modified replacement umbrella 1. A pressure-sensitive adhesive composition containing (1) from tomb) acrylate and a copolymer obtained by copolymerization of a functional group monomer (ii) and (ii) a copolymer obtained by copolymerization of a (meth) acrylate with a radical polymerizable monomer having at least one isocyanate group in its molecule ( B). 2. The pressure-sensitive adhesive composition of claim 1, wherein the copolymer (A) has a weight average molecular weight of between 500,000 and 2,000,000 (based on polystyrene and determined by GPC). 3. The pressure-sensitive adhesive composition of claim 1, wherein the copolymer (B) has a weight average molecular weight of between 50,000 and 1,200,000 (based on polystyrene and determined by GPC). 4. The pressure-sensitive adhesive composition of claim 2, wherein the copolymer (b) has a weight average molecular weight of between 50,000 and 1,200,000 (based on polystyrene and determined by GPC). The pressure-sensitive adhesive composition according to any one of claims 1 to 4, wherein the copolymer (A) is contained in an amount of from 0.1 to 3 parts by weight per mole of the copolymer (b). The pressure-sensitive adhesive composition according to any one of claims 4 to 4, which is for use in an optical element. 7. The pressure-sensitive adhesive composition of claim 5, which is for use in an optical element. 8. An adhesive sheet comprising a layer of the pressure-sensitive adhesive composition according to any one of claims 1 to 7 disposed on at least one side of the substrate sheet. 9. An adhesive optical element comprising the layer of the pressure-sensitive adhesive composition according to any one of claims 1 to 7 wherein at least one of the optical elements of the sheet-like optical element is a polarizing plate' phase difference plate, Anti-reflective sheet or film 96064-1000819.doc 1359180. , οΛ月/严正换页 99064-1000819.doc 2-