KR101260695B1 - Adhesive composition for polarizer and polarizer using the same - Google Patents

Abstract

식 중, Ｍ은 알칼리금속 또는 알칼리토류금속을 나타내고, n은 1 또는 2이다.The adhesive composition for polarizing plates which can improve the outstanding adhesiveness and hot water resistance under humidified heat conditions, and can suppress a Kunic, and the polarizing plate using the same are proposed. The adhesive composition for a polarizing plate proposed includes acetoacetyl group-modified polyvinyl alcohol-based resin, water, an alcohol solvent having a boiling point of 100 ° C. or lower, and glyoxalate represented by the following formula. Acetoacetyl group-modified polyvinyl alcohol-based resin is contained 1 to 8 parts by weight based on 100 parts by weight of water, the solid content weight ratio of acetoacetyl group-modified polyvinyl alcohol-based resin and glyoxalate is 1: 0.03 to 1: 0.25, water The weight ratio of the alcohol solvent to is 99: 1 to 30:70, and the pH is 4 to 10.

In the formula, M represents an alkali metal or an alkaline earth metal, and n is 1 or 2.

Description

Adhesive composition for polarizing plates and polarizing plate using the same {ADHESIVE COMPOSITION FOR POLARIZER AND POLARIZER USING THE SAME}

The present invention relates to an adhesive composition for a polarizing plate and a polarizing plate using the same, and more particularly, to an adhesive composition for a polarizing plate capable of improving excellent adhesiveness and hot water resistance under humidified heat conditions and suppressing the occurrence of niconicity and a polarizing plate using the same. will be.

In the liquid crystal display device, it is indispensable to arrange | position a polarizer on both sides of the glass substrate which forms the liquid crystal panel surface from the image formation system surface. The polarizer is generally obtained by dyeing with a dichroic material such as a polyvinyl alcohol-based film and iodine, then crosslinking using a crosslinking agent, uniaxially stretching to form a film. Since a polarizer is produced by extending | stretching, it is easy to shrink. Moreover, since a polyvinyl alcohol-type film uses a hydrophilic polymer, it is very easy to deform | transform under humid heat conditions especially. In addition, since the mechanical strength of the film itself is weak, there is a problem that the film is torn. Therefore, the polarizing plate which supplemented the intensity | strength by adhering transparent protective films, such as a triacetyl cellulose, to both or one side of a polarizer is used. Such a polarizing plate is manufactured by adhering a polarizer and a transparent protective film with an adhesive agent.

In recent years, the liquid crystal display device has been expanded in use, and has been widely developed from a portable terminal to a large TV for home use. Each standard is formed according to each use. In particular, the use of a portable terminal is assumed to be carried by a user, so the demand for durability is very strict. For example, the polarizing plate is required to have a hot water resistance that does not change its properties and shape even under humidified heat conditions in which dew condensation occurs.

The polarizer is used as a polarizing plate by reinforcing strength by a protective film. As an adhesive for polarizing plates used for adhesion | attachment of a polarizer and a protective film, an aqueous adhesive is preferable, For example, the polyvinyl alcohol-type adhesive agent which mixed the crosslinking agent with the polyvinyl alcohol aqueous solution is used. However, in the case of the polyvinyl alcohol-based adhesive, peeling may occur at the interface between the polarizer and the transparent protective film under the humidified heat condition. This is because the polyvinyl alcohol-based resin, which is the main component of the adhesive, is a water-soluble polymer, and it is conceivable that dissolution of the adhesive occurred under the condensation. In order to solve this problem, the adhesive for polarizing plates containing an acetoacetyl-group modified polyvinyl alcohol-type resin and a crosslinking agent is proposed.

On the other hand, when manufacturing a polarizing plate, when a polarizer and a transparent protective film is bonded through a polyvinyl alcohol-based adhesive, there is a problem that a cunic is generated. Kunic is a local uneven defect occurring at the interface between the polarizer and the transparent protective film. Kunic is particularly likely to occur when acetoacetyl group-modified polyvinyl alcohol-based resin is used as the polyvinyl alcohol-based adhesive. Therefore, there is a demand for the development of an adhesive composition for a polarizing plate which exhibits high adhesion and hot water resistance while suppressing the occurrence of the nic.

The present invention is to solve the above-mentioned problems, an object of the present invention is to provide a polarizing plate adhesive composition and a polarizing plate using the same which can improve the excellent adhesion and hot water resistance under humidified heat conditions, can suppress the occurrence of kunic.

Adhesive composition for polarizing plates according to an aspect of the present invention for achieving the above object is acetoacetyl group-modified polyvinyl alcohol-based resin, water, alcohol solvent having a boiling point of 100 ℃ or less, and glyoxalic acid represented by the following formula 1 to 8 parts by weight of acetoacetyl-group-modified polyvinyl alcohol-based resin, and a solid content weight ratio of acetoacetyl-group-modified polyvinyl alcohol-based resin and glyoxalate based on 100 parts by weight of water. : 0.25, the weight ratio of water and alcohol solvent is 99: 1 to 30:70, and pH is 4-10.

In the formula, M represents an alkali metal or an alkaline earth metal, and n is 1 or 2.

The viscosity of the adhesive composition for polarizing plates is 3-25 mPa * sec.

The alcoholic solvent may be a lower alcohol having 1 to 3 carbon atoms, in particular the alcoholic solvent may be ethanol.

The weight ratio of water and alcohol solvent is preferably 95: 5 to 50:50.

According to another aspect of the present invention, a polarizer and a polarizing plate including a protective film is bonded to at least one side of the polarizer using the adhesive composition for polarizing plate according to one side of the present invention. The protective film may include at least one selected from cellulose resins, cycloolefin resins, polyethylene terephthalate resins, and (meth) acrylate resins.

According to the present invention, since the adhesive strength between the polarizer and the protective film is excellent, excellent adhesion and hot water resistance can be obtained under humidified heat conditions, and since the boiling point contains an alcoholic solvent having a boiling point of 100 ° C. or lower, the occurrence of the kunic is suppressed. . Therefore, the process yield at the time of manufacturing a polarizing plate using the adhesive composition for polarizing plates which concerns on this invention can be improved, and there exists an effect which improves productivity.

Figure 1a is a view showing a polarizing plate before hot water immersion in the water resistance evaluation test method of the polarizing plate manufactured according to an embodiment of the present invention, Figure 1b is a view showing a polarizing plate after hot water immersion.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. However, embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

The adhesive composition for polarizing plates according to the present invention comprises acetoacetyl-group-modified polyvinyl alcohol-based resin, water, an alcohol solvent having a boiling point of 100 ° C. or less, and glyoxalate, and acetoacetyl-group-modified polyvinyl based on 100 parts by weight of water. 1 to 8 parts by weight of alcohol-based resin, the solid content weight ratio of the acetoacetyl-group modified polyvinyl alcohol-based resin and glyoxalate is 1: 0.03 to 1: 0.25, the weight ratio of water and alcohol solvent is 99: 1 to 30 : 70, pH is 4-10.

The adhesive composition for polarizing plates of the present invention is used for a polarizing plate, which is prepared by adhering a protective film to at least one surface of the polarizer and the polarizer. At this time, the adhesive composition for polarizing plates of this invention is apply | coated to either side of a polarizer, and a protective film is adhere | attached.

Although it does not specifically limit as a form of the adhesive composition for polarizing plates, In order to form a uniform adhesive bond layer on the surface of the protective film which is a to-be-adhered body, it is preferable to use as a liquid form. Examples of such liquid adhesives include solutions and dispersion liquids of various solvents. However, in view of coatability to a base material, a solution type is preferable. In view of safety, a solution mainly composed of water is suitably used.

The adhesive composition for polarizing plates contains resin, water, an alcoholic solvent, and a crosslinking agent. Resin used for the adhesive composition for polarizing plates of this invention is acetoacetyl-group modified polyvinyl alcohol-type resin.

Since acetoacetyl-group-modified polyvinyl alcohol-type resin is a polyvinyl alcohol-type adhesive agent which has a highly reactive functional group, when acetoacetyl-group-modified polyvinyl alcohol-type resin is used, durability of a polarizing plate improves.

Acetoacetyl-group-modified polyvinyl alcohol-type resin is obtained by making polyvinyl alcohol-type resin and diketene react by a well-known method. Examples of the polyvinyl alcohol-based resin include polyvinyl alcohol and derivatives thereof obtained by saponifying polyvinyl acetate; Saponified products of copolymers with vinyl acetate and monomers having copolymerizability; And modified polyvinyl alcohol obtained by acetalization, urethaneization, etherification, grafting, or phosphate esterification of polyvinyl alcohol. As said monomer, Unsaturated carboxylic acid, such as maleic anhydride, a fumaric acid, crotonic acid, itaconic acid, (meth) acrylic acid, and its ester; Α-olefins such as ethylene and propylene, (meth) allyl sulfonic acid (soda), sulfonic acid sodium (monoalkyl maleate), disulfonic acid sodium alkyl maleate, N-methylol acrylamide, acrylamide alkyl sulfonic acid alkali salt, N- Vinylpyrrolidone, or N-vinylpyrrolidone derivatives. Polyvinyl alcohol-type resin can use together single 1 type or 2 types or more.

The polyvinyl alcohol-based resin is not particularly limited, but in terms of adhesiveness, the average degree of polymerization is 100 to 5000, preferably 1000 to 4000, and the average degree of saponification is 85 to 100 mol%, preferably 90 to 100. Mol%.

Acetoacetyl group-modified polyvinyl alcohol-type resin is obtained by making a polyvinyl alcohol-type resin and diketene react by a well-known method as mentioned above. Acetoacetyl group-modified polyvinyl alcohol-based resin is, for example, a polyvinyl alcohol-based resin is dispersed in a solvent such as acetic acid, a method of adding diketene thereto, polyvinyl alcohol-based resin is dimethylformamide or dioxane It can melt | dissolve in solvents, such as these previously, and can manufacture using the method of adding diketene here. In addition, a method in which diketene gas or liquid diketene is directly contacted with polyvinyl alcohol can also be used.

The acetoacetyl group modification degree of the acetoacetyl group-modified polyvinyl alcohol-based resin is not particularly limited as long as it is 0.1 mol% or more. When the amount is less than 0.1 mol%, the water resistance of the adhesive layer is insufficient, which is inappropriate. Acetoacetyl group modification degree becomes like this. Preferably it is about 0.1-40 mol%, More preferably, it is 1-20 mol%, Especially preferably, it is 2-7 mol%. When the acetoacetyl group modification degree exceeds 40 mol%, the effect of improving water resistance is small. The degree of acetoacetyl group modification is a value measured by NMR.

The solvent used for the adhesive composition for polarizing plates of this invention is an alcohol solvent whose water and boiling point are 100 degrees C or less. In the present invention, since an alcohol solvent having a very low surface energy in addition to water is used as the solvent, the surface energy of the adhesive is lowered to suppress the occurrence of the Kunic. As the surface energy of the adhesive is lowered, it is possible to eliminate the occurrence of Kunic by filling local irregularities generated at the interface between the polarizer and the protective film.

After coating on the adherend, a drying process is generally performed to remove the solvent contained in the adhesive. However, when the water and the alcohol-based solvent are mixed in the adhesive solution as in the present invention, this drying process can be shortened. The alcohol solvent may have a boiling point lower than that of water, that is, a boiling point of 100 ° C. or lower, in particular 80 ° C. or lower, and 70 ° C. or lower.

The alcohol solvent may be a lower alcohol having 1 to 3 carbon atoms. Specific examples of such alcohol solvents include alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, 1-butanol, or 2-butanol. In particular, the alcohol solvent may be ethanol. Although it does not specifically limit as a compounding quantity of such an alcoholic solvent, As a content ratio (weight ratio) of both in the mixed solvent of water and an alcoholic solvent, it is 99: 1-30: 70, Preferably 95: 5-50: 50 More preferably, the range of 90:10 to 80:20 is suitably used. When there is too much content of an alcoholic solvent, there exists a tendency for the solubility of resin to fall, or the viscosity stability of an adhesive solution to fall, and when it is small, the suppression effect of a Kunic generation may not be acquired.

The crosslinking agent used for the adhesive composition for polarizing plates of this invention is glyoxalate represented by following formula (1).

 In the formula, M represents an alkali metal or an alkaline earth metal, and n is 1 or 2.

Glyoxalate is an alkali metal salt or alkaline earth metal salt of glyoxal acid. Alkali metals and alkaline earth metals are both electronegativity elements, and since their carboxylates have similar chemical properties, they exhibit excellent performance as crosslinking agents of acetacetyl-modified polyvinyl alcohol. Since it is an aldehyde part of glyoxalate, it is estimated that the alkali metal salt and the alkaline earth metal salt of glyoxal acid can acquire the same effect.

Specific examples of the glyoxalate of formula (1) include lithium glyoxalate, sodium glyoxalate, potassium glyoxalate, and the like when M is an alkali metal, and magnesium glyoxalate and glyoxalic acid when M is an alkaline earth metal. Calcium, strontium glyoxalate and barium glyoxalate. Among them, alkali metal salts are preferred in view of being easily soluble in water, and sodium glyoxalate is particularly preferred.

The method for producing glyoxalate is not particularly limited, and a known method can be used, but a method by neutralization of glyoxalic acid with alkali metal hydroxide or alkaline earth metal hydroxide, which is simple to manufacture and easy to purify, is preferable. To be used Can be.

The adhesive composition for polarizing plates of this invention is a solution in which acetoacetyl-group modified polyvinyl alcohol-type resin and glyoxalate are melt | dissolved in the water / alcohol-type solvent mixed solution. In the adhesive composition solution, the concentration of the acetoacetyl group-modified polyvinyl alcohol-based resin may be in the range of 1 to 8 parts by weight based on 100 parts by weight of water. When the concentration of the acetoacetyl-group-modified polyvinyl alcohol-based resin is less than 1 part by weight with respect to 100 parts by weight of water / alcohol mixed solution, the adhesiveness tends to be lowered and the acetoacetyl-group-modified polyvinyl alcohol-based resin When the concentration of is more than 8 parts by weight with respect to 100 parts by weight of water, the optical characteristics of the polarizing plate tend to be lowered. The amount of the acetoacetyl group-modified polyvinyl alcohol-based resin relative to 100 parts by weight of the water / alcohol solvent mixed solution is preferably 5 parts by weight.

The solid content weight ratio of acetoacetyl-group-modified polyvinyl alcohol-type resin and glyoxalate has the glyoxalate of 0.03-0.25 with respect to acetoacetyl-group-modified polyvinyl alcohol-type resin 1. When the weight ratio of glyoxalate to acetoacetyl-modified polyvinyl alcohol-based resin is less than 0.03, it is difficult to sufficiently express the water resistance of the adhesive layer, and the weight ratio of glyoxalate to acetoacetyl-modified polyvinyl alcohol-based resin is When it exceeds 0.25, since the adhesiveness of a polarizing plate falls easily. In addition, it is more preferable that the solid content weight ratio of the acetoacetyl-group-modified polyvinyl alcohol-type resin and glyoxalate in an adhesive composition exists in the range of 1: 0.05-0.2 from a viewpoint of the balance of water resistance and adhesiveness.

In addition, the adhesive composition for polarizing plates uses that pH as 4-10. When the pH of the adhesive composition for polarizing plates is less than 4, it is because water resistance in a polarizing plate state cannot fully be expressed, and when pH of the adhesive composition for polarizing plates exceeds 10, since the pot life of the adhesive aqueous solution for polarizing plates becomes short. to be. It is preferable to make pH of the adhesive composition for polarizing plates 8 or less from a viewpoint of the safety of handling.

It is preferable that the adhesive composition for polarizing plates exists in the range of 3-25 mPa * sec in the viscosity in 20 degreeC. When the viscosity of the adhesive composition for polarizing plates is less than 3 mPa * sec, it is because water resistance in a polarizing plate state cannot fully be expressed, and when a viscosity exceeds 25 mPa * sec, it is because the optical characteristic of a polarizing plate tends to fall.

The adhesive composition for polarizing plates may further contain a water-soluble catalyst. Examples of the water-soluble catalyst that can be used in the present invention include piperazine, pyrrolidinium, zinc chloride, cobalt chloride, magnesium chloride, ammonium chloride, barium oxide, alkyl iodide, and the like. When mix | blending a water-soluble catalyst, it is preferable to make it solid content weight ratio of the catalyst with respect to the acetoacetyl-group-modified polyvinyl alcohol-type resin 1 become 0.005 to 0.2.

The adhesive composition for polarizing plates of this invention can contain additives, such as a plasticizer, a silane coupling agent, an antistatic agent, or a leveling agent, in the range which does not inhibit the effect.

According to another aspect of the present invention, a polarizer and a polarizing plate including a protective film is bonded to at least one side of the polarizer using the adhesive composition for polarizing plate according to one side of the present invention. The polarizing plate of this invention is manufactured by laminating | stacking the protective film containing transparent resin on one or both surfaces of the polarizer containing polyvinyl alcohol-type resin. An adhesive composition, which is an aqueous solution containing acetoacetyl-group-modified polyvinyl alcohol-based resin and glyoxalate, is laminated, and the polarizer film and the protective film are bonded together, followed by drying to form a polarizing plate. Although the thickness of an adhesive bond layer is not specifically limited, Usually, it is 0.0015 micrometer, Preferably it is 0.012 micrometer, More preferably, it is 0.03-0.5 micrometer. When the thickness of an adhesive bond layer exceeds 5 micrometers, the appearance defect of a polarizing plate will generate | occur | produce easily.

The polarizer containing polyvinyl alcohol-type resin is a thing in which the dichroic dye was adsorption-oriented specifically to the uniaxially stretched polyvinyl alcohol-type resin film. Polyvinyl alcohol-type resin which comprises a polarizer can be obtained by saponifying polyvinyl acetate type resin. As polyvinyl acetate type resin, the copolymer etc. of vinyl acetate and the other monomer copolymerizable with it besides the polyvinyl acetate which is a homopolymer of vinyl acetate are illustrated. As another monomer copolymerized with vinyl acetate, unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, vinyl ethers, acrylamide which has an ammonium group, etc. are mentioned, for example. The saponification degree of polyvinyl alcohol-type resin is about 85-100 mol% normally, Preferably it is 98 mol% or more. The polyvinyl alcohol-based resin may be further modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. In addition, the degree of polymerization of the polyvinyl alcohol-based resin is usually about 1,000 to 10,000, preferably about 1,500 to 5,000.

What formed such polyvinyl alcohol-type resin into a film is used as a raw film of a polarizer. The method of forming a polyvinyl alcohol-type resin into a film is not specifically limited, It can form into a film by a well-known method. Although the film thickness of a polyvinyl alcohol-type raw film is not specifically limited, For example, it is about 10 micrometers-150 micrometers.

The polarizer is usually a step of uniaxially stretching such a polyvinyl alcohol-based resin film, a step of dyeing the polyvinyl alcohol-based resin film with a dichroic dye to adsorb the dichroic dye, and a polyvinyl alcohol-based resin to which the dichroic dye is adsorbed. It manufactures through the process of processing a film with aqueous solution of boric acid, and the process of washing with water after the process by aqueous solution of boric acid.

Uniaxial stretching may be performed before dyeing, simultaneously with dyeing, or after dyeing. When performing uniaxial stretching after dyeing, uniaxial stretching may be performed before boric acid treatment, or may be performed during boric acid treatment. Of course, it is also possible to uniaxially stretch in these several steps. As uniaxial stretching, the method etc. which extend | stretch uniaxially between the rolls from which a circumferential speed differs, etc. can be employ | adopted, for example. Moreover, the method of extending | stretching uniaxially using a heat roll, and extending | stretching, such as extending | stretching in air | atmosphere, may be sufficient, and the wet extending | stretching which extends in the state swelled with a solvent may be sufficient. A draw ratio is about 3 to 8 times normally.

In order to dye a polyvinyl alcohol-type resin film with a dichroic dye, it is preferable to immerse a polyvinyl alcohol-type resin film in the aqueous solution containing a dichroic dye, for example. Specific examples of the dichroic dye include iodine and dichroic organic dyes. In addition, it is preferable that the polyvinyl alcohol-based resin film be immersed in water before the dyeing treatment.

When using iodine as a dichroic dye, the method of immersing and dyeing a polyvinyl alcohol-type resin film in the aqueous solution containing iodine and potassium iodide is employ | adopted normally. The content of iodine in this aqueous solution is usually about 0.01 to 1 part by weight per 100 parts by weight of water, and the content of potassium iodide is usually about 0.5 to 20 parts by weight per 100 parts by weight of water. The temperature of the aqueous solution used for dyeing is about 20-40 degreeC normally, and the immersion time (dyeing time) in this aqueous solution is about 20-1,800 second normally. On the other hand, when using a dichroic organic dye as a dichroic dye, the method of immersing and dyeing a polyvinyl alcohol-type resin film in the aqueous solution containing water-soluble colored organic dye is employ | adopted normally. The content of the dichroic organic dye in the aqueous solution for dyeing is usually 1 × 10 ^-4 to 10 parts by weight, preferably 1 × 10 ^-3 to 1 part by weight based on 100 parts by weight of water. The aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing aid. The temperature of the dye aqueous solution used for dyeing is about 20-80 degreeC normally, and the immersion time (dyeing time) in this aqueous solution is about 10 to 1,800 second normally.

The boric acid treatment after dyeing with a dichroic dye is performed by immersing the dyed polyvinyl alcohol-type resin film in boric acid containing aqueous solution. The amount of boric acid in the boric acid-containing aqueous solution is usually 2 to 15 parts by weight, preferably 5 to 12 parts by weight, per 100 parts by weight of water. When iodine is used as a dichroic dye, it is preferable that this boric acid containing aqueous solution contains potassium iodide. The amount of potassium iodide in the aqueous solution containing boric acid is usually 0.1 to 15 parts by weight, preferably 5 to 12 parts by weight, per 100 parts by weight of water. Immersion time in boric acid containing aqueous solution is 60 to 1,200 second normally, Preferably it is 150 to 600 second, More preferably, it is 200 to 400 second. The temperature of boric acid containing aqueous solution is 50 degreeC or more normally, Preferably it is 50-85 degreeC, More preferably, it is 60-80 degreeC.

The polyvinyl alcohol-based resin film after boric acid treatment is usually washed with water. The water washing process is performed by immersing the polyvinyl alcohol-type resin film processed by boric acid in water, for example. The temperature of water in a water washing process is 5 to 40 degreeC normally, and immersion time is 1 to 120 second normally. After washing with water, a drying treatment is performed to obtain a polarizer. A drying process is normally performed using a hot air dryer or a far infrared heater. The drying treatment temperature is usually 30 to 100 ° C, preferably 50 to 80 ° C. The drying treatment time is usually 60 to 600 seconds, and preferably 120 to 600 seconds. In this manner, the polyvinyl alcohol-based resin film is subjected to uniaxial stretching, dyeing with a dichroic dye, and boric acid treatment to obtain a polarizer. The thickness of this polarizer is 5-40 micrometers.

As a material which forms the protective film adhered to one or both surfaces of a polarizer, it is preferable that it is excellent in transparency, mechanical strength, thermal stability, moisture barrier property, and isotropy. The protective film may include at least one selected from cellulose resins, cycloolefin resins, polyethylene terephthalate resins, and (meth) acrylate resins.

For example, the protective film may be a polyester polymer such as polyethylene terephthalate or polyethylene naphthalate, a cellulose polymer such as diacetyl cellulose or triacetyl cellulose, an acrylic polymer such as polymethyl methacrylate, polystyrene or acrylonitrile. Styrene-type polymers, such as a styrene copolymer (AS resin), a polycarbonate-type polymer, etc. are mentioned. Further, polyethylene, polypropylene, polyolefins having a cyclo- or norbornene structure, polyolefin-based polymers such as ethylene-propylene copolymers, amide-based polymers such as vinyl chloride-based polymers, nylon and aromatic polyamides, imide-based polymers, and sulfides Phone polymer, polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, allylate polymer, polyoxymethylene polymer, Epoxy-based polymers, blends of the polymers, etc. may also be mentioned as examples of the polymer forming the transparent protective film.

In addition, although a transparent protective film is adhere | attached normally by an adhesive bond layer to a polarizer, thermosetting resins, such as a (meth) acrylic-type, a urethane type, an acrylurethane type, an epoxy type, a silicone type, or a ultraviolet curable resin, can be used as a transparent protective film. One or more types of arbitrary appropriate additives may be contained in the transparent protective film. As an additive, a ultraviolet absorber, antioxidant, a lubricating agent, a plasticizer, a mold release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment, or a coloring agent is mentioned, for example. Content of the thermoplastic resin in a transparent protective film becomes like this. Preferably it is 50-100 weight%, More preferably, it is 50-99 weight%, More preferably, it is 60-98 weight%, Especially preferably, it is 70-97 weight%. When content of the thermoplastic resin in a transparent protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has may not be fully expressed.

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by these examples. % And parts which show content-usage-amount below are a basis of weight unless there is particular notice.

Example 1

(a) Preparation of polarizer

Polyvinyl alcohol film having an average degree of polymerization of about 2,400, a degree of saponification of at least 99.9 mol%, and a thickness of 75 μm was uniaxially stretched by about 5 times in a dry manner, and was kept in pure water at 60 ° C. in a stretched state. After immersion for 5 minutes, it was immersed at 28 degreeC for 60 second in the aqueous solution whose weight ratio of iodine / potassium iodide / water is 0.05 / 5/100. Thereafter, the solution was immersed at 72 ° C. for 300 seconds in an aqueous solution having a weight ratio of potassium iodide / boric acid / water of 8.5 / 8.5 / 100. Subsequently, the resultant was washed with pure water at 26 ° C. for 20 seconds, and then dried at 65 ° C. to prepare a polarizer in which iodine was adsorbed on a polyvinyl alcohol film.

(b) Preparation of Adhesive Composition

Acetoacetyl-group-modified polyvinyl alcohol-based resin (trade name "Cosenole Z200", Nippon Synthetic Chemical Industry Co., Ltd., 4% aqueous solution viscosity 12.5 mPasec, saponification degree 99.5 mol%) is dissolved in pure water, and concentration is 10% An aqueous solution of was prepared. Acetoacetyl group-modified polyvinyl alcohol-type resin aqueous solution and sodium glyoxalate which is a crosslinking agent are mixed so that the former: latter solid content weight ratio may be 1: 0.1. Ethanol is used as the alcohol solvent, so that the water / alcohol mixed solvent has a weight ratio of 90:10 and 100 parts of water / alcohol mixed solvent such that acetoacetyl group-modified polyvinyl alcohol-based resin is 1 part. Dilution with to prepare an adhesive composition. This composition had a pH of 5.7 and a viscosity of 3.5 mPasec.

(c) Preparation of Polarizer

After apply | coating the adhesive composition from the process (b) to both surfaces of the polarizer produced at the process (a), the protective film was bonded. This was dried for 3 minutes at 60 degreeC temperature, and the polarizing plate was produced. (Thickness of adhesive layer: about 0.1 micrometer).

Example 2

An adhesive composition was prepared in the same manner as in Example 1 (b), except that the acetoacetyl-modified polyvinyl alcohol-based resin was diluted to 3 parts with 100 parts of water / alcohol mixed solvent to dilute with a water / alcohol mixed solvent. . This composition had a pH of 5.6 and a viscosity of 7.5 mPa · sec. Except having used this composition, the polarizing plate was produced like the (c) process of Example 1.

EXAMPLE 3

An adhesive composition was prepared in the same manner as in Example 1 (b), except that the acetoacetyl-modified polyvinyl alcohol-based resin was diluted with 5 parts of the water / alcohol mixture to 100 parts of the water / alcohol mixture solvent. . This composition had a pH of 5.6 and a viscosity of 17.0 mPa · sec. Except having used this composition, the polarizing plate was produced like the (c) process of Example 1.

EXAMPLE 4

Acetoacetyl-group-modified polyvinyl alcohol-type resin in the process of Example 1 (b): The solid content weight ratio of sodium glyoxalate is 1: 0.05, and acetoacetyl-group-modified polyvinyl alcohol-type resin with respect to 100 parts of water / alcohol mixture solvents An adhesive composition was prepared in the same manner as in Example 1 (b) except that the mixture was diluted with a water / alcohol mixed solvent so as to be 3 parts. This composition had a pH of 5.6 and a viscosity of 7.4 mPa · sec. Except having used this composition, the polarizing plate was produced like the (c) process of Example 1.

EXAMPLE 5

Acetoacetyl-group modified polyvinyl alcohol-type resin in the process of Example 1 (b): The solid content weight ratio of sodium glyoxalate shall be 1: 0.2, and acetoacetyl-group-modified polyvinyl alcohol-type resin with respect to 100 parts of water / alcohol mixture solvents An adhesive composition was prepared in the same manner as in Example 1 (b) except that the dilution was carried out with a water / alcohol mixed solvent to add 3 parts. PH of this composition was 5.5 and the viscosity was 7.5 mPa * sec. Except having used this composition, the polarizing plate was produced like the (c) process of Example 1.

[Example 6]

In step (b) of Example 1, 100 parts of the water / alcohol mixed solvent is diluted with water / alcohol mixed solvent such that the acetoacetyl-modified polyvinyl alcohol-based resin is 3 parts, where the weight ratio of the water / alcohol mixed solvent Adhesive composition was prepared in the same manner except that was adjusted to 99: 1. This composition had a pH of 5.5 and a viscosity of 7.4 mPa · sec. Except having used this composition for this composition, the polarizing plate was produced like the (c) process of Example 1.

[Example 7]

In step (b) of Example 1, 100 parts of the water / alcohol mixed solvent is diluted with water / alcohol mixed solvent such that the acetoacetyl-modified polyvinyl alcohol-based resin is 3 parts, where the weight ratio of the water / alcohol mixed solvent An adhesive composition was prepared in the same manner except that was adjusted to 30:70. This composition had a pH of 5.6 and a viscosity of 7.7 mPasec. Except having used this composition for this composition, the polarizing plate was produced like the (c) process of Example 1.

[Example 8]

In the step (b) of Example 1, acetoacetyl-group-modified polyvinyl alcohol-based resin was referred to as "Cosenol Z100 (trade name, Nippon Synthetic Chemical Industries, Ltd., 4% aqueous solution viscosity 5.2 mPasec, saponification degree 99.2 mol%). A 5% concentration aqueous solution was prepared, and this acetoacetyl-group-modified polyvinyl alcohol-based resin aqueous solution and sodium glyoxalate serving as a crosslinking agent were mixed so that the former solid weight ratio of the latter was 1: 0.1. The weight ratio of the solvent was diluted with water / alcohol mixed solvent so that the acetoacetyl group-modified polyvinyl alcohol-based resin was 3 parts with respect to 90:10 and 100 parts of the water / alcohol mixed solvent to prepare an adhesive composition. , pH was 5.6 and viscosity was 3.2 mPa · sec.

[Example 9]

In the step (b) of Example 1, acetoacetyl-group-modified polyvinyl alcohol-based resin was referred to as "Cosenol Z300 (trade name, Nippon Synthetic Chemical Co., Ltd., 4% aqueous solution viscosity 27.9 mPasec, saponification degree 98.5 mol%). A 5% concentration aqueous solution was prepared, and this acetoacetyl-group-modified polyvinyl alcohol-based resin aqueous solution and sodium glyoxalate serving as a crosslinking agent were mixed so that the former solid weight ratio of the latter was 1: 0.1. The weight ratio of the solvent was diluted with water / alcohol mixed solvent so that the acetoacetyl group-modified polyvinyl alcohol-based resin was 3 parts with respect to 90:10 and 100 parts of the water / alcohol mixed solvent to prepare an adhesive composition. , pH was 5.6 and viscosity was 12.0 mPa · sec.

[Comparative Example 1]

In step (b) of Example 1, 100 parts of the water / alcohol mixed solvent is diluted with water / alcohol mixed solvent such that the acetoacetyl-modified polyvinyl alcohol-based resin is 3 parts, where the weight ratio of the water / alcohol mixed solvent The adhesive composition was prepared in the same manner except that 20 was adjusted to 20:80. PH of this composition was 5.5 and the viscosity was 7.8 mPa * sec. Except having used this composition for this composition, the polarizing plate was produced like the (c) process of Example 1.

[Comparative example 2]

In step (b) of Example 1, 100 parts of the water / alcohol mixed solvent is diluted with water / alcohol mixed solvent such that the acetoacetyl-modified polyvinyl alcohol-based resin is 3 parts, where the weight ratio of the water / alcohol mixed solvent The adhesive composition was prepared in the same manner except that 9 was adjusted to 99.5: 0.5. PH of this composition was 5.5 and the viscosity was 7.8 mPa * sec. Except having used this composition for this composition, the polarizing plate was produced like the (c) process of Example 1.

[Comparative Example 3]

In step (b) of Example 1, dilute the water / alcohol mixture with 3 parts of acetoacetyl-group-modified polyvinyl alcohol-based resin with respect to 100 parts of the water / alcohol mixture solvent, and adjust the pH to 11 using sodium hydroxide as an additive. An adhesive composition was produced in the same manner except that the composition was adjusted to. This composition had a pH of 11.0 and a viscosity of 7.8 mPasec. Except having used this composition, it carried out similarly to thing (c) of Example 1, and produced the polarizing plate.

[Comparative Example 4]

In step (b) of Example 1, 100 parts of the water / alcohol mixed solvent is diluted with water / alcohol mixed solvent so that the acetoacetyl-modified polyvinyl alcohol-based resin is 3 parts, and the pH is adjusted to 3 using acetic acid as an additive. The adhesive composition was produced similarly except having adjusted. This composition had a pH of 3.0 and a viscosity of 7.8 mPasec. A polarizing plate was produced in the same manner as in Example 1 (c) except that the composition was used.

[Comparative Example 5]

Acetoacetyl-group modified polyvinyl alcohol-type resin in the process of Example 1 (b): The solid content weight ratio of sodium glyoxalate shall be 1: 0.5, and acetoacetyl-group-modified polyvinyl alcohol-type resin with respect to 100 parts of water / alcohol mixture solvents An adhesive composition was prepared in the same manner as in Example 1 (b) except that the mixture was diluted with a water / alcohol mixed solvent so as to be 3 parts. This composition had a pH of 5.7 and a viscosity of 7.5 mPa · sec. Except having used this composition, the polarizing plate was produced like the (c) process of Example 1.

[Comparative Example 6]

Acetoacetyl-group modified polyvinyl alcohol-type resin in the process of Example 1 (b): The solid content weight ratio of sodium glyoxalate is 1: 0.02, and acetoacetyl-group-modified polyvinyl alcohol-type resin with respect to 100 parts of water / alcohol mixture solvents An adhesive composition was prepared in the same manner as in Example 1 (b) except that the mixture was diluted with a water / alcohol mixed solvent so as to be 3 parts. This composition had a pH of 5.7 and a viscosity of 7.5 mPa · sec. Except having used this composition, the polarizing plate was produced like the (c) process of Example 1.

[Comparative Example 7]

An adhesive composition was prepared in the same manner as in Example 1 (b), except that the acetoacetyl-modified polyvinyl alcohol-based resin was diluted to 0.5 parts with respect to 100 parts of water / alcohol mixed solvent to dilute the water / alcohol mixed solvent. did. This composition had a pH of 5.8 and a viscosity of 2.5 mPasec. Except having used this composition, the polarizing plate was produced like the (c) process of Example 1.

[Comparative Example 8]

An adhesive composition was prepared in the same manner as in Example 1 (b), except that the acetoacetyl-modified polyvinyl alcohol-based resin was diluted with 10 parts of water / alcohol mixture to 100 parts of water / alcohol mixed solvent. did. This composition had a pH of 5.8 and a viscosity of 2.5 mPasec. Except having used this composition, the polarizing plate was produced like the (c) process of Example 1.

[Comparative Example 9]

The crosslinking agent was changed to glyoxal, the solid content weight ratio of acetoacetyl-group-modified polyvinyl alcohol-based resin (Cosenol Z200) and glyoxal was 1: 0.2, and acetoacetyl-group-modified polyvinyl per 100 parts of water / alcohol mixed solvent. The adhesive composition was manufactured like Example (b) of Example 1 except having diluted with the water / alcohol mixture solvent so that alcohol resin may be 3 parts. PH of this composition was 5.3 and the viscosity was 7.6 mPa * sec. Except having used this composition, the polarizing plate was produced like the (c) process of Example 1.

[Comparative Example 10]

The crosslinking agent was changed to boric acid, the solid content weight ratio of acetoacetyl-group modified polyvinyl alcohol-based resin (Cosenol Z200) and boric acid was 1: 0.2, and acetoacetyl group-modified polyvinyl alcohol-based was added to 100 parts of water / alcohol mixed solvent. An adhesive composition was prepared in the same manner as in Example (b) except that the resin was diluted with a water / alcohol mixed solvent so that the resin was 3 parts. PH of this composition was 5.3 and the viscosity was 7.6 mPa * sec. Except having used this composition, the polarizing plate was produced like the (c) process of Example 1.

Table 1 below shows the resins, crosslinking agent solvents and additives used in Examples 1 to 9 and Comparative Examples 1 to 10, their contents, and the physical properties of the adhesive composition for polarizing plates produced.

Suzy Cross-linking agent solvent additive Properties Kinds Solvent: Resin Kinds Resin: Crosslinking agent Water: Alcohol - pH Viscosity Example 1 Z200 100: 1 Sodium glyoxalate 1: 0.1 90:10 - 5.7 3.5 Example 2 Z200 100: 3 Sodium glyoxalate 1: 0.1 90:10 - 5.6 7.5 Example 3 Z200 100: 5 Sodium glyoxalate 1: 0.1 90:10 - 5.6 17.0 Example 4 Z200 100: 3 Sodium glyoxalate 1: 0.05 90:10 - 5.6 7.4 Example 5 Z200 100: 3 Sodium glyoxalate 1: 0.2 90:10 - 5.5 7.5 Example 6 Z200 100: 3 Sodium glyoxalate 1: 0.1 99: 1 - 5.5 7.4 Example 7 Z200 100: 3 Sodium glyoxalate 1: 0.1 30:70 - 5.6 7.7 Example 8 Z100 100: 3 Sodium glyoxalate 1: 0.1 90:10 - 5.6 3.2 Example 9 Z300 100: 3 Sodium glyoxalate 1: 0.1 90:10 - 5.6 12.0 Comparative Example 1 Z200 100: 3 Sodium glyoxalate 1: 0.1 20:80 - 5.5 7.8 Comparative Example 2 Z200 100: 3 Sodium glyoxalate 1: 0.1 99.5: 0.5 - 5.5 7.8 Comparative Example 3 Z200 100: 3 Sodium glyoxalate 1: 0.1 90:10 Sodium hydroxide 11.0 7.8 Comparative Example 4 Z200 100: 3 Sodium glyoxalate 1: 0.1 90:10 Acetic acid 3.0 7.8 Comparative Example 5 Z200 100: 3 Sodium glyoxalate 1: 0.5 90:10 - 5.7 7.5 Comparative Example 6 Z200 100: 3 Sodium glyoxalate 1: 0.02 90:10 - 5.7 7.5 Comparative Example 7 Z200 100: 0.5 Sodium glyoxalate 1: 0.1 90:10 - 5.8 2.5 Comparative Example 8 Z200 100: 10 Sodium glyoxalate 1: 0.1 90:10 - 5.8 2.5 Comparative Example 9 Z200 100: 3 Glyoxal 1: 0.2 90:10 - 5.3 7.6 Comparative Example 10 Z200 100: 3 Boric acid 1: 0.2 90:10 - 5.3 7.6

[Evaluation examination]

The following evaluation tests were done about each polarizing plate obtained from Examples 1-10 and Comparative Examples 1-10.

[1] Adhesiveness (cutter evaluation)

After leaving each polarizing plate at room temperature for 1 hour, a cutter blade is placed between each film of the polarizing plate (between the polarizer and the protective film A and between the polarizer and the protective film B) and the method of entering the blade when the blade is pushed out is as follows. Evaluation was made based on the criteria.

○: The blade of the cutter does not enter between any films.

(Triangle | delta): When pushing on a blade, it stops when a blade enters 4-5 mm between at least one film.

X: When pushing on a blade, a blade enters between at least one film without difficulty (when a blade enters between one film without difficulty, a blade does not enter the other side, or 4-5 mm stops when entered).

[2] hot water resistance

The following hot water resistance test (hot water immersion test) was performed about each polarizing plate left to stand for 24 hours in 23 degreeC and the environment of 55% of relative humidity, and water resistance was evaluated. First, a polarizing plate was cut into a rectangular shape of 5 cm × 2 cm with the absorption axis (stretching direction) of the polarizing plate as the long side, a sample was produced, and the dimension of the long side direction was measured correctly. Here, the sample exhibits a unique color uniformly over the entire surface due to iodine adsorbed to the polarizer.

Figure 1a is a view showing a polarizing plate before hot water immersion in the water resistance evaluation test method of the polarizing plate prepared according to Example 1 of the present invention, Figure 1b is a view showing a polarizing plate after hot water immersion. As shown in FIG. 1A, one short side of the sample was gripped by the holding part 2, and about 80% in the longitudinal direction was immersed in a 60 ° C water bath and maintained for 4 hours. Then, the polarizing plate 1 was taken out from the water tank, and the moisture was wiped off.

The polarizer 5 of the polarizing plate contracted by hot water immersion is shown in FIG. 1B. The shrinkage degree of the polarizer 5 is evaluated by measuring the distance from the tip 1 '(end of the protective film) of the polarizing plate 1 to the end of the contracted polarizer 5 in the center of the short side of the polarizing plate 1. This was taken as the shrinkage length. In addition, as shown in FIG. 1B, the polarizer 5 positioned in the middle of the polarizing plate contracts by warm water immersion, thereby forming a polarizer absence region 3, which is a region where the polarizer 5 does not exist between the protective films. .

Moreover, iodine elutes from the periphery of the polarizer 5 which contacts hot water by hot water immersion, and the area | region 4 in which the color fell out in the periphery of the polarizing plate 1 is produced. This discoloration degree was evaluated by measuring the distance from the tip of the contracted polarizer 5 in the center of the short side of the polarizing plate 1 to the area | region where the color peculiar to a polarizing plate remains, and was made into iodine stripping length. The sum of the shrinkage length and the iodine omission length was taken as the total erosion length (X). That is, the total erosion length X is the distance from the end 1 '(end of the protective film) of the polarizing plate 1 at the center of the short side of the polarizing plate 1 to the region in which the color peculiar to the polarizing plate remains. . It can be judged that the smaller the shrinkage length, the iodine elimination length and the total erosion length X, the higher the adhesion (water resistance) in the presence of water. The criteria are as follows.

◎: Total erosion length 미만 is less than 2 mm.

○: total erosion length 침 is 2 mm or more but less than 3 mm.

(Triangle | delta): Total erosion length (Ｘ) is 3 mm or more and less than 5 mm.

×: total erosion length Ｘ is 5 mm or more.

[3] Appearance evaluation (bad poor)

The polarizing plate was cut out so that it might be set to 1000 mm x 1000 mm, and the sample polarizing plate was produced. The sample polarizer was placed under a fluorescent lamp. On the light source side of the sample polarizing plate, another polarizing plate was provided so that each absorption axis might go straight, and in this state, the number of the points (conic defect) which light leaks was counted.

(Double-circle): The number of Kunic defects is less than three.

(Circle): The number of Kunic defects is three or more and less than ten.

(Triangle | delta): The number of Kunic defects is 10 or more and less than 20

X: The number of Kunic defects is 20 or more.

[4] polarization degree

The polarization degree Py measures the parallel transmittance (H0) and the orthogonal transmittance (H90) of a polarizer using an ultraviolet visible spectrophotometer (The Nippon Bunco Co., Ltd. make, brand name "V-7100 / VAP-7070"), FIG. (%) = was calculated by _{{(H 0 -H 90) /} (H 0 + H 90)} 1/2 × 100. These transmittance | permeability are Y values which corrected visibility by the 2 degree visual field (C light source) prescribed | regulated to JISZ 8701 (1982 edition). The result was evaluated as follows.

○: Py is 99.996% or more.

(Triangle | delta): Py is more than 99.993% and less than 99.996%.

X: Py is 99.993% or less.

The results of the evaluation test are shown in Table 2.

Adhesive Hot water resistance Polarization degree Unwell Other properties Example 1 ○ ◎ ○ ○ - Example 2 ○ ◎ ○ ○ - Example 3 ○ ◎ ○ ○ - Example 4 ○ ○ ○ ○ - Example 5 ○ ◎ ○ ○ - Example 6 ○ ◎ ○ ○ - Example 7 ○ ◎ ○ ○ - Example 8 ○ ◎ ○ ○ - Example 9 ○ ◎ ○ ○ - Comparative Example 1 - - ○ - Phase separation Comparative Example 2 ○ ◎ ○ △ - Comparative Example 3 ○ ◎ ○ ○ Potlife × Comparative Example 4 ○ △ ○ ◎ - Comparative Example 5 △ ◎ △ ○ - Comparative Example 6 ○ △ ○ ○ - Comparative Example 7 ○ △ ○ △ - Comparative Example 8 ○ ◎ △ △ - Comparative Example 9 △ △ △ ○ - Comparative Example 10 ○ × ○ ○ -

Referring to Table 2, Comparative Example 1 in which the weight ratio of the alcohol solvent in the mixed solvent in the adhesive composition is too high, the compatibility of the acetoacetyl-modified polyvinyl alcohol-based resin is poor phase separation, the weight ratio of alcohol is too low The polarizing plate of Example 2 had a low effect of improving the puncture defect.

Comparative Example 3 having a high pH of the adhesive composition had a short pot life (lifetime that can be used as an adhesive), and Comparative Example 4 having a low pH did not exhibit sufficient water resistance. The comparative example 5 which made the ratio of the crosslinking agent high did not show sufficient polarization degree, and the comparative example 6 which made the ratio of the crosslinking agent low was not showing sufficient water resistance.

Comparative Example 7 having a low concentration of acetoacetyl-group-modified polyvinyl alcohol-based resin in the adhesive composition did not have sufficient water resistance, and Comparative Example 8 having a high concentration of polyvinyl alcohol-based resin did not show sufficient polarization degree. Moreover, the comparative examples 9 and 10 using the well-known crosslinking agent were the performance which neither polarization nor adhesiveness was enough.

Therefore, the polarizing plates of Comparative Examples 1 to 10 having high or low content of alcohol solvent, pH of composition, type and content ratio of crosslinking agent, and resin content, etc. are poor in performance, but are manufactured according to the present invention. It was confirmed that the polarizing plates of Examples 1 to 9 exhibited excellent performances in adhesiveness, hot water resistance, polarization degree, Kunic defect, and other physical properties.

The invention is not to be limited by the foregoing embodiments and the accompanying drawings, but should be construed by the appended claims. In addition, it will be apparent to those skilled in the art that various forms of substitution, modification, and alteration are possible within the scope of the present invention without departing from the technical spirit of the present invention.

1 polarizer
1 'polarizer bottom
2 grip
3 polarizer absent region
4 color missing areas
5 polarizer
X erosion length

Claims (7)

Acetoacetyl group-modified polyvinyl alcohol-based resin, water, an alcohol solvent having a boiling point of 100 ° C. or less, and glyoxalate represented by the following chemical formula,
1 to 8 parts by weight of the acetoacetyl-group-modified polyvinyl alcohol-based resin with respect to 100 parts by weight of water, wherein the solid content weight ratio of the acetoacetyl-group-modified polyvinyl alcohol-based resin and the glyoxalate is 1: 0.03 to 1: Adhesive composition for a polarizing plate is 0.25, the weight ratio of the water and the alcohol solvent is 99: 1 to 30:70, pH 4 to 10:

In the formula, M represents an alkali metal or an alkaline earth metal, and n is 1 or 2. The method according to claim 1,
The viscosity in 20 degreeC of the said adhesive composition for polarizing plates is 3-25 mPa * sec, The adhesive composition for polarizing plates characterized by the above-mentioned. The method according to claim 1,
The alcohol solvent is a lower alcohol having 1 to 4 carbon atoms adhesive composition for a polarizing plate. The method according to claim 1,
The alcohol solvent is ethanol, the adhesive composition for a polarizing plate. The method according to claim 1,
Adhesive composition for polarizing plates, characterized in that the weight ratio of the water and the alcohol solvent is 95: 5 to 50:50. A polarizer and a polarizing plate comprising a protective film adhered to at least one surface of the polarizer using the adhesive composition for a polarizing plate according to any one of claims 1 to 5. The method of claim 6,
The protective film is a polarizing plate comprising at least one selected from cellulose resins, cycloolefin resins, polyethylene terephthalate resins and (meth) acrylate resins.

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