TWI491697B - Adhesive composition and surface protection film - Google Patents

Description

Adhesive composition and surface protective film

The present invention relates to a surface protective film used in a manufacturing step of a liquid crystal display. More specifically, the present invention relates to an adhesive composition for a surface protective film which is adhered to a surface of an optical member such as a polarizing plate or a retardation film which constitutes a liquid crystal display, and which protects the surface of an optical member such as a polarizing plate or a retardation film. And a surface protective film using the same.

In the manufacturing steps of an optical member such as a polarizing plate or a phase difference plate constituting a liquid crystal display, the surface protective film is temporarily adhered to the surface of the optical member. When the optical member is assembled in the liquid crystal display, the surface protective film is peeled off from the optical member and removed. The surface protective film for protecting the surface of the optical member is generally referred to as a step film since it is used only in the manufacturing step.

The surface protective film used in the step of producing the optical member is formed on one surface of an optically transparent polyethylene terephthalate (PET) resin film to form an adhesive layer. Further, the release-treated release film for protecting the adhesive layer is adhered to the upper surface of the adhesive layer until it is adhered to the optical member.

In addition, an optical member such as a polarizing plate or a retardation film is subjected to optical evaluation of the display capability, chromaticity, contrast, and impurity incorporation of the liquid crystal display panel in a state in which the surface protective film is adhered. Inspection, therefore, the necessary properties of the surface protective film are that no bubbles or impurities adhere to the adhesive layer.

Further, in recent years, it is necessary to prevent the antistatic property of generating static electricity when the surface protective film is peeled off from an optical member such as a polarizing plate or a phase difference plate. The reason for this is that when the adhesive layer is peeled off from the adherend, there is a possibility that the electrification at the time of peeling due to the generated static electricity may cause the electrical control circuit of the liquid crystal display to malfunction.

In addition, when the surface protective film is adhered to an optical member such as a polarizing plate or a retardation plate, the surface protective film may be temporarily peeled off and the surface protective film may be reattached for various reasons. At this time, a surface protective film which is easily peeled off from the optical member of the adherend (having reworkability) is required.

Further, when the surface protective film is peeled off from an optical member such as a polarizing plate or a phase difference plate, it is required to be able to be quickly peeled off. That is, in order to perform peeling quickly even by peeling at a high speed, it is required that the adhesive force is less affected by the peeling speed.

As described above, in recent years, the performances of the following (1) to (4) are required as the required performance of the adhesive layer constituting the surface protective film.

(1) Under low-speed peeling and high-speed peeling, a balance of adhesion is obtained.

(2) It can prevent the occurrence of adhesive residue.

(3) It has excellent antistatic properties.

(4) Has rework performance.

However, although the required performance of each of (1) to (4) can be satisfied, it is still extremely difficult to have all of the required performances of (1) to (4) required for the adhesive layer of the surface protective film.

For example, the following proposals are known regarding (1) obtaining a balance of adhesion under low-speed peeling and high-speed peeling; and (2) preventing occurrence of adhesive residue.

An acrylic resin obtained by crosslinking a copolymer of an alkyl (meth)acrylate having a carbon number of 7 or less and a copolymerizable compound having a carboxyl group as a main component and crosslinking the mixture by a crosslinking agent The adhesive is a problem that the adhesive adheres to the side of the adherend after a long time of sticking, and the adhesive force of the adherend rises with time. In order to prevent this problem, an adhesive (pressure-sensitive adhesive) is known which uses an alkyl (meth)acrylate having an alkyl group having 8 to 10 carbon atoms and a copolymerizable compound having an alcoholic hydroxyl group. The copolymer is obtained by crosslinking treatment with a crosslinking agent (Patent Document 1).

Further, an adhesive or the like is proposed, and a copolymer of a (meth)acrylic acid alkyl ester and a carboxyl group-containing copolymerizable compound is blended in a small amount in the same copolymer as described above, and a crosslinking agent is used for crosslinking treatment. . However, when it is used for surface protection of a plastic plate having a low surface tension and a smooth surface, there is a problem of peeling due to lifting during processing or storage, or high-speed peeling by manual peeling. The problem of poor peelability.

In order to solve such problems, an adhesive composition is proposed which is based on (a) an alkyl (meth) acrylate having an alkyl (meth) acrylate having an alkyl group having 8 to 10 carbon atoms as a main component. 100 parts by weight of the base ester is prepared by adding (b) 1 to 15 parts by weight of a carboxyl group-containing copolymerizable compound and 3 to 100 parts by weight of (c) a vinyl ester of an aliphatic carboxylic acid having 1 to 5 carbon atoms. a copolymer of a monomer mixture and compounding the carboxyl group relative to the above component (b) in the copolymer A crosslinking agent or more (Patent Document 2).

The adhesive composition described in Patent Document 2 does not have a peeling phenomenon such as floating during processing or storage, and the adhesion time rises little, and the releasability is excellent, even after long-term storage, special It is a long-term storage in a high-temperature environment, and can be further peeled off with a small force. At this time, no adhesive residue is generated on the adherend, and re-peeling can be performed with a small force even when high-speed peeling is performed.

Further, regarding (3) having excellent antistatic properties, as a method of imparting antistatic properties to a surface protective film, a method of mixing an antistatic agent into a base film has been disclosed. As the antistatic agent, various cationic antistatic agents having (a) a cationic group having a quaternary ammonium salt, a pyridinium salt, a mono- to tertiary amino group or the like; (b) having a sulfonate group or a sulfate salt have been disclosed. An anionic antistatic agent such as an anion group such as a phosphate group, a phosphate group or a phosphonate group; (c) an amphoteric antistatic agent such as an amino acid or an amine sulfate; (d) an amino alcohol system and glycerin (e) a nonionic antistatic agent such as a polyethylene glycol system; (e) a polymer type antistatic agent obtained by polymerizing an antistatic agent as described above (Patent Document 3).

Further, in recent years, it has been proposed not only to include such an antistatic agent in a base film or to apply it to a surface of a base film, but also to directly include it in an adhesive layer.

In addition, (4) has a rework property, for example, an adhesive composition is proposed, which is a curing agent for dissolving an isocyanate compound in an acrylic resin in an amount of 0.0001 to 10 parts by weight based on 100 parts by weight of the acrylic resin. Specific phthalate oligomer (Patent Document 4).

In Patent Document 4, an alkyl acrylate having an alkyl group having a carbon number of about 2 to 12, an alkyl methacrylate having an alkyl group having a carbon number of about 4 to 12, or the like is used as a main monomer component. For example, a monomer component containing another functional group such as a carboxyl group-containing monomer may be contained. In general, it is preferable to contain 50% by weight or more of the above-mentioned main monomer, and the content of the monomer component containing a functional group is 0.001 to 50% by weight, preferably 0.001 to 25% by weight, more preferably 0.01 to 25% by weight. %. The adhesive composition described in Patent Document 4 has a small effect on the cohesive force and the adhesive force over a high temperature or a high temperature and high humidity, and exhibits an excellent effect on the curved surface adhesion force, and thus has reworkability.

In general, if the adhesive layer is made into a flexible property, adhesive residue is likely to occur, and reworkability is also likely to be lowered. That is, it is difficult to peel off when it is affixed incorrectly, and it is difficult to re-stick. Therefore, it is necessary to crosslink the monomer having a functional group such as a carboxyl group to the main agent, and to form the adhesive layer with a certain hardness so as to have reworkability.

[Patent Document 1] Japanese Patent Laid-Open Publication No. SHO 63-225677

[Patent Document 2] Japanese Patent Laid-Open No. Hei 11-256111

[Patent Document 3] Japanese Patent Laid-Open No. Hei 11-070629

[Patent Document 4] Japanese Patent Laid-Open No. Hei 8-199130

In the prior art, as an adhesive layer constituting a surface protective film Performance requirements: Balance of adhesion, excellent antistatic properties, and rework at low speed peeling and high speed peeling. However, although it is possible to individually satisfy the individual required performance, it is still impossible to satisfy all the required performances required for the adhesive layer of the surface protective film.

The present invention has been made in view of the above circumstances. An object of the present invention is to provide an adhesive composition and a surface protective film which have antistatic properties, are excellent in balance of adhesion under low-speed peeling and high-speed peeling, and are excellent in durability, reworkability, and antistatic property.

In order to solve the above problems, the present invention provides an adhesive composition comprising (A) a (meth) acrylate monomer having an alkyl group having C4 to C10, (B) a hydroxy group-containing copolymerizable monomer, (C) a copolymer of a carboxyl group-containing copolymerizable monomer and (D) a polyalkylene glycol mono(meth)acrylate monomer, and further containing (E) a trifunctional or higher isocyanate compound, (F) a crosslinking inhibitor, (G) a crosslinking catalyst, (H) an antistatic agent, and (I) a polyether modified oxirane compound.

The (B) hydroxyl group-containing copolymerizable monomer is selected from the group consisting of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (methyl). a group of compounds consisting of 2-hydroxyethyl acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide At least one or more; preferably, the (A) (C) hydroxyl group-containing (C)-C10 (meth) acrylate monomer contains 0.1 to 5.0 parts by weight of the above (B) hydroxyl group. Copolymerizable monomer, and, on In the (B) hydroxyl group-containing copolymerizable monomer, the total amount of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate is 0. ~0.9 parts by weight.

The (C) carboxyl group-containing copolymerizable monomer is at least one selected from the group consisting of (meth)acrylic acid, carboxyethyl (meth)acrylate, and carboxypentyl (meth)acrylate. It is preferred to contain 0.35 to 1.0 part by weight of the above (C) carboxyl group-containing copolymerizable monomer with respect to 100 parts by weight of the (A) alkyl group having a C4 to C10 (meth) acrylate monomer. body.

The (D) polyalkylene glycol mono(meth)acrylate monomer is selected from the group consisting of polyalkylene glycol mono(meth)acrylate, methoxypolyalkylene glycol (meth)acrylate, and ethoxylated polymer. At least one or more of the compound group consisting of alkanediol (meth) acrylate; preferably a (meth) acrylate having a C4 to C10 carbon number with respect to 100 parts by weight of the above (A) alkyl group The monomer contains 1 to 20 parts by weight of the above (D) polyalkylene glycol mono(meth)acrylate monomer.

The above (E) trifunctional or higher isocyanate compound is an addition member of a trimer isocyanate selected from a hexamethylene diisocyanate compound, a isocyanurate of an isophorone diisocyanate compound, and a hexamethylene diisocyanate compound. At least one or more of a compound composition of an isophorone diisocyanate compound, a biuret of a hexamethylene diisocyanate compound, and a biuret compound of an isophorone diisocyanate compound, The above-mentioned (E) trifunctional or higher isocyanate compound is contained in an amount of 0.5 to 5.0 parts by weight based on 100 parts by weight of the above copolymer.

The above (H) antistatic agent preferably contains 0.1 to 5.0 parts by weight of an ionic compound having a melting point of 30 to 80 ° C with respect to 100 parts by weight of the above copolymer, or 0.1 to 5.0 by weight in the above copolymer. % copolymerized, quaternary ammonium salt type acrylic monomer having a melting point of 30 to 80 °C.

The polyether-modified polyoxane compound of the above (I) is a polyether-modified oxirane compound having an HLB value of 7 to 12, preferably 0.01 to 0.5 part by weight based on 100 parts by weight of the above copolymer. The above (I) polyether modified oxirane compound.

The (F) crosslinking inhibitor is a ketoenol tautomer compound, and preferably contains 1.0 to 5.0 parts by weight of the above (F) crosslinking inhibitor with respect to 100 parts by weight of the above copolymer.

The (G) cross-linking catalyst is an organotin compound, and preferably contains 0.01 to 0.5 part by weight of the above (G) cross-linking catalyst based on 100 parts by weight of the copolymer.

Preferably, the adhesive layer obtained by crosslinking the above adhesive composition has an adhesive force of 0.05 to 0.1 N/25 mm at a low-speed peeling speed of 0.3 m/min, and an adhesive force of 1.0 at a high-speed peeling speed of 30 m/min. N/25mm or less.

It is preferable that the surface resistivity of the adhesive layer obtained by crosslinking the above-mentioned adhesive composition is 5.0 × 10 ^{+ 10} Ω / □ or less, and the peeling tape voltage is ± 0 to 1 kV.

Further, the present invention provides an adhesive film formed by crosslinking an adhesive composition of the above-described adhesive composition on one surface or both surfaces of a resin film.

Moreover, the present invention provides a surface protective film which will enable the above adhesive group The adhesive layer formed by cross-linking the product is formed on one surface of the resin film, and is peeled and adhered by a steel ball pen after being adhered to the surface protective film of the adherend through the adhesive layer. Body, no migration to the adherend.

As the above surface protective film, use as a surface protective film of a polarizing plate can be used.

It is preferable to carry out antistatic and anti-pollution treatment on the surface of the resin film opposite to the side on which the above-mentioned adhesive layer is formed.

According to the present invention, it is possible to satisfy all the properties required for the adhesive layer of the surface protective film which have not been solved by the prior art. In addition, excellent performance against antistatic properties and prevention of residual glue can be obtained. Specifically, it is possible to reduce the amount of the antistatic agent added while maintaining the antistatic property, and further improve the performance of preventing the occurrence of residual glue.

Hereinafter, the present invention will be described based on preferred embodiments.

The adhesive composition of the present invention is characterized in that the main component is a copolymerizable monomer containing (A) a (meth) acrylate monomer having an alkyl group having C4 to C10, and (B) a hydroxyl group. And (C) a copolymer of a carboxyl group-containing copolymerizable monomer and (D) a polyalkylene glycol mono(meth)acrylate monomer, and further containing (E) a trifunctional or higher isocyanate compound, (F) a crosslinking inhibitor, (G) a crosslinking catalyst, (H) an antistatic agent, and (I) a polyether modified siloxane compound.

As (A) a (meth) acrylate single having an alkyl group having a carbon number of C4 to C10 The body may, for example, be butyl (meth)acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (methyl) ) octyl acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate Wait.

The (B) hydroxyl group-containing copolymerizable monomer may, for example, be 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate, ( (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl methacrylate, N-hydroxy(methyl) acrylamide, N-methylol (meth) acrylamide, N-hydroxyl A hydroxyl group-containing (meth) acrylamide such as a (meth) acrylamide or the like.

Preferably, it is selected from the group consisting of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N At least one or more of a group consisting of hydroxy (meth) acrylamide, N-methylol (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide.

It is preferable to contain 0.1 to 5.0 parts by weight of the above (B) hydroxyl group-containing copolymerizable monomer with respect to 100 parts by weight of the (A) (C)-C10-C10 (meth) acrylate monomer. .

Further, in (B) a hydroxyl group-containing copolymerizable monomer, a total amount of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate Preferably, it is less than 1 part by weight (may not be contained), and Good 0~0.9 parts by weight.

Preferably, the (C) carboxyl group-containing copolymerizable monomer is at least one selected from the group consisting of (meth)acrylic acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate. the above.

It is preferable to contain 0.35 to 1.0 part by weight of (C) a carboxyl group-containing copolymerizable monomer with respect to 100 parts by weight of the (A) alkyl group having a C4 to C10 (meth) acrylate monomer.

The (D) polyalkylene glycol mono(meth)acrylate monomer may be a compound in which one of the plurality of hydroxyl groups of the polyalkylene glycol is esterified to a (meth)acrylate. Since the (meth) acrylate group becomes a polymerizable group, it can be copolymerized to the main agent polymer. The other hydroxyl group may be maintained as OH, or may be an alkyl ether such as methyl ether or diethyl ether or a saturated carboxylic acid ester such as acetate.

The alkylene group which the polyalkylene glycol has may be, for example, an ethyl group, a propyl group or a butyl group, but is not limited thereto. The polyalkylene glycol may be a copolymer of two or more kinds of polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of the copolymer of the polyalkylene glycol include polyethylene glycol-polypropylene glycol, polyethylene glycol-polybutylene glycol, polypropylene glycol-polybutylene glycol, and polyethylene glycol-polypropylene glycol-polybutylene glycol. Alternatively, the copolymer may be a block copolymer or a random copolymer.

The (D) polyalkylene glycol mono(meth)acrylate monomer is preferably selected from the group consisting of polyalkylene glycol mono(meth)acrylate, methoxypolyalkylene glycol (meth)acrylate, and B. At least one or more of the compound groups consisting of oxypolyalkylene glycol (meth) acrylates.

More specifically, for example, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, polyethylene glycol-poly Propylene glycol-mono(meth)acrylate, polyethylene glycol-polybutylene glycol-mono(meth)acrylate, polypropylene glycol-polybutylene glycol-mono(meth)acrylate, polyethylene glycol-poly Propylene glycol-polybutylene glycol-mono(meth)acrylate; methoxypolyethylene glycol-(meth)acrylate, methoxypolypropylene glycol-(meth)acrylate, methoxypolybutylene glycol -(Meth)acrylate, methoxy-polyethylene glycol-polypropylene glycol-(meth)acrylate, methoxy-polyethylene glycol-polybutylene glycol-(meth)acrylate, methoxy Poly-propylene glycol-polybutylene glycol-(meth)acrylate, methoxy-polyethylene glycol-polypropylene glycol-polybutylene glycol-(meth)acrylate; ethoxylated polyethylene glycol-( Methyl) acrylate, ethoxypolypropylene glycol-(meth) acrylate, ethoxylated polybutylene glycol-(meth) acrylate, ethoxy-polyethylene glycol-polypropylene glycol-(methyl) Acrylate, ethoxy-polyethylene glycol-polybutylene glycol-(meth)acrylate Ethoxy - glycol - polyethylene glycol - (meth) acrylate, ethoxy - polyethylene glycol - polypropylene glycol - polyethylene glycol - (meth) acrylate.

It is preferred to contain 1 to 20 parts by weight of the above (D) polyalkylene glycol monomer with respect to 100 parts by weight of the (A) alkyl group having a C4 to C10 (meth) acrylate monomer. Methyl) acrylate monomer.

The (E) trifunctional or higher isocyanate compound may be a polyisocyanate compound having at least three or more isocyanate (NCO) groups in one molecule, and examples thereof include hexamethylene diisocyanate and isophorone diisocyanate. , Biuret modified or trimerized isocyanate of diisocyanate such as diphenylmethane diisocyanate, toluene diisocyanate or dylyl diisocyanate (compound having 2 NCO groups in one molecule) An addition object (polyol modified substance) of a trivalent or higher polyvalent alcohol (a compound having at least three or more OH groups in one molecule) such as trimethylolpropane or glycerin.

(E) The trifunctional or higher isocyanate compound is a polyisocyanate compound having at least three or more isocyanate (NCO) groups in one molecule, and particularly preferably a trimeric isocyanate selected from a hexamethylene diisocyanate compound, and isophor. A trimeric isocyanate of a keto diisocyanate compound, an addition object of a hexamethylene diisocyanate compound, an addition object of an isophorone diisocyanate compound, a biuret body of a hexamethylene diisocyanate compound, and an isophor At least one or more of the compound groups consisting of biuret bodies of the keto diisocyanate compound. The (E) trifunctional or higher isocyanate compound is preferably contained in an amount of 0.5 to 5.0 parts by weight based on 100 parts by weight of the copolymer.

Examples of the (F) crosslinking inhibitor include methyl ethyl acetate, ethyl acetate, octyl acetate, oleyl acetate, lauryl acetate, and stearyl acetate. A β-ketoester such as an ester, or a β-diketone such as acetamidineacetone, 2,4-hexanedione or benzamidineacetone. These are ketoenol tautomer compounds, and in the adhesive composition using a polyisocyanate compound as a crosslinking agent, by fixing the isocyanate group which the crosslinking agent has, it is possible to suppress the adhesive agent after the crosslinking agent is blended. The excessive viscosity of the composition rises or gels, prolonging the shelf life of the adhesive composition.

(F) The crosslinking inhibitor is preferably a ketoenol tautomer compound, and particularly preferably at least one selected from the group consisting of acetamidineacetone and ethyl acetate.

It is preferred to contain 1.0 to 5.0 parts by weight of (F) a crosslinking inhibitor with respect to 100 parts by weight of the copolymer.

In the case where the polyisocyanate compound is used as the crosslinking agent, the (G) crosslinking catalyst may have a function as a catalyst for the reaction (crosslinking reaction) between the copolymer and the crosslinking agent, and for example, An organometallic compound such as an amine compound such as a tertiary amine, an organotin compound, an organic lead compound or an organozinc compound.

Examples of the tertiary amine include a trialkylamine, N,N,N',N'-tetraalkyldiamine, N,N-dialkylamino alcohol, and tri-ethylenediamine. Phenanthene derivative Derivatives, etc.

Examples of the organotin compound include a dialkyl tin oxide, a fatty acid salt of a dialkyl tin, a fatty acid salt of stannous, and the like.

(G) The crosslinking catalyst is preferably an organotin compound, and particularly preferably at least one selected from the group consisting of dioctyltin oxide and dioctyltin dilaurate.

It is preferred to contain 0.01 to 0.5 part by weight of the (G) crosslinking catalyst with respect to 100 parts by weight of the copolymer.

(H) The antistatic agent is preferably solid at normal temperature (for example, 30 ° C), more specifically, preferably 100 parts by weight of the above copolymer, and the content is 0.1 to 5.0 parts by weight of an ionic compound having a melting point of 30 to 80 ° C or a quaternary ammonium salt type acrylic monomer having a melting point of 30 to 80 ° C in a copolymer of 0.1 to 5.0% by weight. In the present invention, as the (H) antistatic agent, (H1) an ionic compound having a melting point of 30 to 80 ° C or a quaternary ammonium salt type acrylic monomer having a (H 2 ) melting point of 30 to 80 ° C is added to the copolymer. Copolymerized in the copolymer. Since these (H) antistatic agents have a low melting point and a long-chain alkyl group, it is presumed that the affinity with the acrylic copolymer is high.

The ionic compound having a (H1) melting point of 30 to 80 ° C is an ionic compound having a cation and an anion, and examples thereof include the following compounds: a cation is a pyridinium cation, an imidazolium cation, a pyrimidine cation, a pyrazolium cation, or the like. a nitrogen-containing phosphonium cation such as a pyrrolidine cation or an ammonium cation, or a compound such as a phosphonium cation or a sulfonium cation; the anion is a hexafluorophosphate (PF ₆ ^- ), a thiocyanate (SCN ^- ), an alkylbenzene sulfonate; A compound of an inorganic or organic anion such as an acid radical (RC ₆ H ₄ SO ₃ ^- ), perchlorate (ClO ₄ ^- ), or tetrafluoroborate (BF ₄ ^- ). A material having a melting point of 30 to 80 ° C can be obtained by selecting the chain length of the alkyl group or the position and number of the substituent. The cation is preferably a quaternary nitrogen-containing cerium cation, and examples thereof include a 4-alkylpyridinium cation (a 2- to 6-position carbon atom which may have a substituent or an unsubstituted), and a 1,3-second cation. A quaternary ammonium cation such as a quaternary imidazolium cation such as a tetraimidazolium group (having a substituent or a non-substituted carbon atom at the 2, 4 or 5 position) or a tetraalkylammonium group.

The quaternary ammonium salt type acrylic monomer having a (H2) melting point of 30 to 80 ° C is an ionic compound having a cation and an anion, and examples thereof include the following compounds: a cation is a (meth) propylene decyloxyalkyltriane a (meth)acrylic group-containing quaternary ammonium compound such as a radical ammonium (R ₃ N ⁺ -C _n H _2n -OCOCQ=CH ₂ , wherein Q=H or CH ₃ , R=alkyl), an anion of six Inorganic or fluorinated phosphate (PF ₆ ^- ), thiocyanate (SCN ^- ), organic sulfonate (RSO ₃ ^- ), perchlorate (ClO ₄ ^- ), tetrafluoroborate (BF ₄ ^- ) A compound of an organic anion.

Specific examples of the (H) antistatic agent are not particularly limited, and examples thereof include 1-octylpyridinium hexafluorophosphate, 1-mercaptopyridinium hexafluorophosphate, and 2-methyl-1. - dodecylpyridinium hexafluorophosphate, 1-octylpyridinium dodecylbenzenesulfonate, 1-dodecylpyridinium thiocyanate, 1-dodecylpyridinium ten Dialkylbenzenesulfonate, 4-methyl-1-octylpyridinium hexafluorophosphate, dimethylaminomethyl acrylate hexafluorophosphate methyl salt [(CH ₃ ) ₃ N ⁺ CH ₂ OCOCH=CH ₂ ‧PF ₆ ^- ] and so on.

(I) Polyether-modified siloxane compound is a polyether-based oxirane compound having a polyether-based oxime in addition to the usual oxime unit (-SiR ¹ ₂ -O-) Oxytomane unit [-SiR ¹ (R ² O(R ³ O) _n R ⁴ )-O-]. Here, R ¹ represents one or two or more alkyl groups or aryl groups, R ² and R ³ represent one or two or more kinds of alkylene groups, and R ⁴ represents one or two or more kinds of alkyl groups and hydrazines. Base or the like (end group). The polyether group may, for example, be a polyoxyalkylene group such as a polyoxyalkylene group ((C ₂ H ₄ O) _n ) or a polyoxylated propyl group ((C ₃ H ₆ O) _n ).

(I) a polyether-modified siloxane compound is a polyether-modified oxirane compound having an HLB value of 7 to 12, preferably based on 100 parts by weight of the above copolymer. The naphthene compound modified with 0.01 to 0.5 part by weight of the above (I) polyether is contained. More preferably, it is 0.1 to 0.5 part by weight.

The HLB is, for example, a hydrophilic-lipophilic balance (ratio of hydrophilicity to lipophilicity) prescribed in JIS K3211 (surfactant terminology).

The polyether-modified oxane compound is, for example, a polyorganosiloxane chain having a decyl group, and an organic compound having an unsaturated bond and a polyoxyalkylene group is grafted by a hydroquinone reaction. . Specifically, for example, dimethyloxane. Methyl (polyethylene oxide) alkane copolymer, dimethyl methoxy alkane. Methyl (polyoxyethylene) oxirane. Methyl (polyoxypropylene) siloxane copolymer, dimethyl methoxy alkane. A methyl (polyoxypropylene) siloxane copolymer or the like.

The adhesion and reworkability of the adhesive can be improved by blending the (I) polyether modified naphthenic compound into the adhesive composition.

Further, as another component, a copolymerizable (meth)acrylic monomer, a (meth)acrylamide monomer, a dialkyl-substituted acrylamide monomer, and an interfacial activity containing an alkylene oxide can be appropriately formulated. A known additive such as a agent, a hardening accelerator, a plasticizer, a filler, a hardening inhibitor, a processing aid, an anti-aging agent, and an antioxidant. These may be used alone or in combination of two or more.

The copolymer of the main component used in the adhesive composition of the present invention can be copolymerized by (A) a (meth) acrylate monomer having an alkyl group having a carbon number of C4 to C10 and (B) a hydroxyl group-containing copolymer. The monomer, (C) a carboxyl group-containing copolymerizable monomer, and (D) a polyalkylene glycol mono(meth)acrylate monomer are polymerized and synthesized. The polymerization method of the copolymer is not particularly limited, and solution polymerization, emulsion polymerization, or the like can be used. Proper polymerization method.

In the case of using the (H2) quaternary ammonium salt type acrylic monomer as the (H) antistatic agent, the copolymer of the main agent used in the adhesive composition of the present invention can be obtained by using (A) an alkane a (meth) acrylate monomer having a carbon number of C4 to C10, (B) a copolymerizable monomer having a hydroxyl group, (C) a carboxyl group-containing copolymerizable monomer, and (D) a polyalkylene glycol single (A) The acrylate monomer is synthesized by polymerization with a quaternary ammonium salt type acrylic monomer of (H2).

The (E) trifunctional or higher isocyanate compound, (F) crosslinking inhibitor, (G) crosslinking catalyst, (H) antistatic agent, (I) polyether modified hydrazine are blended in the above copolymer. The adhesive composition of the present invention can be prepared by using an oxane compound and an appropriate optional additive. Further, when a quaternary ammonium salt type acrylic monomer having a (H2) melting point of 30 to 80 ° C is polymerized in a copolymer of a main component, the (H) antistatic agent may not be further added to the copolymer.

Preferably, the adhesive layer obtained by crosslinking the above adhesive composition has an adhesive force of 0.3 to 0.1 N/25 mm at a low-speed peeling region of 0.3 m/min, and an adhesive force of 1.0 N/min at a high-speed peeling region of 30 m/min. 25mm or less. As a result, it is possible to obtain a performance in which the adhesive force has little change with the peeling speed, and even if it is peeled at a high speed, peeling can be performed quickly. Further, in order to re-stick, the surface protective film is temporarily peeled off, and an excessive force is not required, and it is easy to peel off from the adherend.

It is preferable that the surface resistivity of the adhesive layer obtained by crosslinking the above-mentioned adhesive composition is 5.0 × 10 ^{+ 10} Ω / □ or less, and the peeling tape voltage is ± 0 to 1 kV. Further, in the present invention, "±0 to 1 kV" means 0 to -1 kV and 0 to +1 kV, that is, -1 to +1 kV. When the surface resistivity is large, the performance of the electrostatic gas generated by the static electricity is poor when it is peeled off. Therefore, when the surface resistivity is sufficiently reduced, the adhesive layer is peeled off from the adherend. The peeling static voltage accompanying the generated electrostatic gas is reduced, and the influence on the electrical control circuit of the adherend or the like can be suppressed.

The gel fraction of the adhesive layer (adhesive after crosslinking) obtained by crosslinking the adhesive composition of the present invention is preferably 95 to 100%. Thus, since the gel fraction is high, the adhesion in the low-speed peeling region can be prevented from becoming excessive, the dissolution of the unpolymerized monomer or oligomer from the copolymer is lowered, and the reworkability and high temperature are improved. Durability in high humidity, inhibiting contamination by adherends.

The adhesive film of the present invention is formed by forming an adhesive layer obtained by crosslinking the adhesive composition of the present invention on one surface or both surfaces of a resin film. Further, the surface protective film of the present invention is a surface protective film in which an adhesive layer obtained by crosslinking the adhesive composition of the present invention is formed on one surface of a resin film. In the adhesive composition of the present invention, since the components (A) to (I) are blended in a well-balanced manner, the antistatic property is provided, and the balance of the adhesive force is excellent in the low-speed peeling region and the high-speed peeling region, and is durable. Sexuality and reworkability (after being adhered to the surface protective film of the adherend via the above-mentioned adhesive layer, and drawn by a steel ball pen, it is peeled off by the adherend, and no migration to the adherend occurs) It is also excellent in electrostatic properties. Therefore, the surface protective film of the present invention can be used as a surface protective film of a polarizing plate.

a base film as an adhesive layer and a release film (separator) for protecting an adhesive surface A resin film or the like of a polyester film or the like is used.

In the base film, antifouling treatment by an fluorenone-based, fluorine-based release agent, coating agent, cerium oxide fine particles or the like can be performed on the surface of the resin film opposite to the side on which the adhesive layer layer is formed. Antistatic treatment by application or kneading of an antistatic agent.

In the release film, a release treatment by an anthrone or a fluorine-based release agent is applied to the surface of the pressure-sensitive adhesive layer on the side to which the adhesive surface is adhered.

[Examples]

Hereinafter, the present invention will be specifically described based on examples.

<Preparation of acrylic acid copolymer> [Example 1]

Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, and the air in the reaction apparatus was replaced with nitrogen. Then, 100 parts by weight of 2-ethylhexyl acrylate, 0.9 parts by weight of 8-hydroxyoctyl acrylate, 0.5 parts by weight of acrylic acid, 3 parts by weight of polyethylene glycol monoacrylate, and a solvent (ethyl acetate) were added to the reaction apparatus. 60 copies. Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise thereto over 2 hours, and the mixture was reacted at 65 ° C for 6 hours to obtain an acrylic copolymer solution used in Example 1 having a weight average molecular weight of 500,000. 1.

[Examples 2 to 9 and Comparative Examples 1 to 9]

The acrylic copolymer solution 1 used in the above Example 1 was prepared except that the composition of the monomer was set as shown in Tables 1 (A) to (D), respectively. In the same manner, the acrylic copolymer solutions used in Examples 2 to 9 and Comparative Examples 1 to 9 were obtained.

<Preparation of Adhesive Composition and Surface Protective Film> [Example 1]

As described above, for the acrylic copolymer solution 1 produced (in which the acrylic copolymer was 100 parts by weight), 1.5 parts by weight of 1-octylpyridinium hexafluorophosphate, KF-351A (polyether of HLB=12) was added. 0.1 parts by weight of a modified oxoxane compound, and 2.5 parts by weight of acetamidine acetone, and stirred, then added 1.5 parts by weight of CORONATE HX (trimeric isocyanate of hexamethylene diisocyanate compound), dioctyltin dilaurate 0.02 The parts by weight were mixed with stirring to obtain the adhesive composition of Example 1. The adhesive composition was applied onto a release film composed of an oxime resin coated polyethylene terephthalate (PET) film, and then dried at 90 ° C to remove the solvent to obtain an adhesive layer. Adhesive sheet having a thickness of 25 μm.

Then, the adhesive sheet is transferred to the opposite surface of the antistatic and antifouling treatment of the antistatic and antifouling treated polyethylene terephthalate (PET) film on one side, and The surface protective film of Example 1 having a laminated structure of a PET film/adhesive layer/release film (PET film coated with an oxime resin) which is antistatic and antifouling treatment.

[Examples 2 to 9 and Comparative Examples 1 to 9]

The composition of the additive was carried out in the same manner as in the surface protective film of Example 1 except that the composition of the additive was as described in (E) to (I) of Table 1, respectively. The surface protective films of Examples 2 to 9 and Comparative Examples 1 to 9.

In Table 1, the blending ratio of each component is a numerical value obtained by adding 100 parts by weight of the total of the group (A), and is represented by a bracket. Further, the compound names of the respective components used in Table 1 are shown in Table 2. In addition, CORONATE (registered trademark) HX and HL are trade names of Japan POLYURETHANE INDUSTRIAL CO., LTD.; TAKENATE (registered trademark) D-140N is the trade name of Mitsui Chemicals Co., Ltd.; DURANATE (registered trademark) 24A-100 is Asahi Kasei Chemicals The trade names of the company limited by shares; KF-351A, KF-352A, KF-353, KF-640 and X-22-6191 are the trade names of Shin-Etsu Chemical Co., Ltd.

<Test method and evaluation>

The surface protective films of Examples 1 to 9 and Comparative Examples 1 to 9 were aged for 7 days in an environment of 23° C. and 50% RH, and then the release film was peeled off (coated with an anthrone resin). The PET film) was used as a measurement sample for the gel fraction and surface resistivity to expose the adhesive layer.

Further, the surface protective film exposing the adhesive layer is adhered to the surface of the polarizing plate adhered to the liquid crystal cell via the adhesive layer, and left for 1 day, and then subjected to autoclaving at 50 ° C, 5 atm, and 20 minutes. The mixture was further allowed to stand at room temperature for 12 hours, and this was used as a measurement sample for adhesion, peeling static voltage, and durability.

<gel fraction>

After the aging was completed, the mass of the measurement sample before sticking to the polarizing plate was accurately measured, and after immersing in toluene for 24 hours, it was filtered by a metal mesh of 200 mesh. Then, after drying the filtrate at 100 ° C for 1 hour, the mass of the residue was accurately measured, and the gel fraction of the adhesive layer (adhesive after crosslinking) was calculated from the following formula.

Gel fraction (%) = insoluble portion (g) / adhesive quality (g) × 100

<adhesion>

The following peel strength was used as the adhesive force: the test sample obtained above was peeled off at a low speed (0.3 m/min) and a high speed (30 m/min) in the direction of 180° using a tensile tester (25 mm adhered to the surface of the polarizing plate) Peel strength measured by a wide surface protection film).

<surface resistance>

After aging, the adhesive film was exposed by peeling off the release film (PET film coated with an oxime resin) before sticking to the polarizing plate, and the adhesive layer was measured using a resistivity meter Hiresta UP-HT450 (manufactured by Mitsubishi Chemical Corporation) Table Surface resistivity.

<peeling static voltage>

When the measurement sample obtained above was peeled off at a tensile rate of 180° at a tensile rate of 30 m/min, a high-precision electrostatic sensor SK-035, SK-200 (manufactured by KEYENCY Co., Ltd.) was used to measure the voltage (static voltage) generated by the polarizing plate due to static electricity. The maximum value measured was taken as the peeling static voltage.

<reworkability>

After drawing on the surface protective film of the measurement sample obtained above by a steel ball pen (loading 500 g, reciprocating three times), the surface protective film was peeled off from the polarizing plate, and the surface of the polarizing plate was observed, and the presence or absence of contamination of the polarizing plate was confirmed. The evaluation target is based on the case where the polarizing plate is not polluted, and is set to "○". When the contamination is traced along at least a part of the trajectory drawn by the ballpoint pen, it is evaluated as "△", and the trajectory drawn along the ballpoint pen is evaluated. It was confirmed that the contamination was transferred, and the adhesion of the adhesive was confirmed from the surface of the adhesive to be "x".

<Durability>

The measurement sample obtained above was placed in an environment of 60 ° C and 90% RH for 250 hours, and then taken out at room temperature. After further standing for 12 hours, the adhesion was measured, and it was confirmed that it was not significantly different from the initial adhesion. increase. The evaluation target standard was evaluated as "○" when the adhesion after the test was 1.5 times or less of the initial adhesive force, and "x" when the adhesion was more than 1.5 times.

The evaluation results are shown in Table 3. Further, the surface resistivity is expressed by a method in which "m × 10 ^{+ n} " is "mE + n" (where m is an arbitrary real number and n is a positive integer).

The surface protective films of Examples 1 to 9 had an adhesive force of 0.3 to 0.1 N/25 mm at a low-speed peeling region of 0.3 m/min, and an adhesive force of 1.0 N/25 mm or less at a high-speed peeling region of 30 m/min, and the surface resistivity was 5.0×10 ⁺¹⁰ Ω/□ or less, the stripping voltage is ±0~1Kv, and there is no migration to the adherend after being drawn on the surface protective film by the steel ball pen through the adhesive layer, 60°C, 90%RH Durability is also excellent when placed in an environment for 250 hours.

In other words, (1) the adhesion at the low speed and the adhesion at the high speed are obtained, (2) the occurrence of the adhesive residue can be prevented, and (3) Superior antistatic properties, and (4) all required performance with reworkability.

The surface protective film of Comparative Example 1 may have a low adhesion at a low-speed peeling region of 0.3 m/min and a slight reworkability because it does not contain (D) a polyalkylene glycol mono(meth)acrylate monomer.

In the surface protective film of Comparative Example 2, (B) the hydroxyl group-containing monomer is too small, (D) the polyalkylene glycol mono(meth)acrylate monomer is too small, (E) the isocyanate compound is excessive, and (I) is aggregated. The HLB value of the ether-modified oxirane compound is too small, so the adhesion of the low-speed peeling zone of 0.3 m/min and the adhesion of the high-speed peeling zone of 30 m/min become excessive, the peeling withstand voltage is high, and the reworkability and durability are deteriorated. The gel fraction is low.

In the surface protective film of Comparative Example 3, (B) the monomer having a hydroxyl group was excessive, (C) the acid-containing monomer was excessive, and (D) the polyalkylene glycol mono(meth)acrylate monomer was excessive (I). The polyether-modified helioxane compound has an excessively large HLB value. Therefore, the low-speed peeling region has a low adhesion of 0.3 m/min, a high surface resistivity, a high peeling withstand voltage, and poor durability.

In the surface protective film of Comparative Example 4, since (C) the acid-containing monomer was too small and the (D) polyalkylene glycol mono(meth)acrylate monomer was not contained, the adhesion at a low-speed peeling region of 0.3 m/min was possible. Low force, poor rework and durability.

In the surface protective film of Comparative Example 5, there may be a case where (B) a monomer having a hydroxyl group is excessive, (D) a polyalkylene glycol mono(meth)acrylate monomer is too small, and (E) an isocyanate compound is too small, so that a low-speed peeling region may be used. The adhesion force of 0.3 m/min and the adhesion force of 30 m/min in the high-speed peeling area become too large, and the peeling withstand voltage is high, The reworkability and durability are deteriorated, and the gel fraction is lowered.

In the surface protective film of Comparative Example 6, since the (F) crosslinking inhibitor and the (G) crosslinking catalyst were excessively mixed, the storage period was too short, and crosslinking was performed before coating, and coating was impossible.

The surface protective film of Comparative Example 7 may contain too much MA having a C1 alkyl group in (A) a (meth) acrylate monomer having an alkyl group, (B) a monomer having a hydroxyl group, and no (D) poly Alkanediol mono(meth)acrylate monomer, unmixed (G) cross-linking catalyst, so the adhesion of 0.3m/min in the low-speed peeling area and the adhesion of 30m/min in the high-speed peeling area are too large, and the surface resistivity is high. High peeling withstand voltage, poor reworkability and durability.

In the surface protective film of Comparative Example 8, there may be a case where the (D) polyalkylene glycol mono(meth)acrylate monomer is excessive and the (I) polyether modified naphthene compound is not formulated, so the low-speed peeling region is 0.3 m. The adhesion of /min and the high-speed peeling zone have an excessive adhesion force of 30 m/min, a high surface resistivity, a high peeling withstand voltage, and poor reworkability.

In the surface protective film of Comparative Example 9, the melting point of the (D) polyalkylene glycol mono(meth)acrylate monomer and the (H) superstatic agent may be less than 30 ° C (liquid at normal temperature), ( I) The polyether-modified polyoxane compound is too much, so the adhesion at a low-speed peeling region of 0.3 m/min is low, the peeling withstand voltage is high, the reworkability is slightly poor, and the durability is poor.

As described above, in the surface protective films of Comparative Examples 1 to 9, it was not possible to simultaneously satisfy (1) the adhesion balance in the low-speed peeling and the high-speed peeling, and (2) the adhesion preventing agent. The occurrence of residual glue, (3) superior antistatic properties, and (4) all required performance with reworkability.

Claims (16)

An adhesive composition comprising (A) a (meth) acrylate monomer having an alkyl group having C4 to C10, (B) a hydroxy group-containing copolymerizable monomer, and (C) a carboxyl group; a copolymer of a comonomer and a (D) polyalkylene glycol mono(meth)acrylate monomer, which further contains (E) a trifunctional or higher isocyanate compound and (F) a ketoenol tautomer compound a cross-linking inhibitor, (G) a cross-linking catalyst, (H) an antistatic agent, (I) a polyether-modified oxirane compound adhesive composition, wherein, relative to 100 parts by weight of the above (A a (meth) acrylate monomer having an alkyl group having a carbon number of C4 to C10, each containing 0.1 to 5.0 parts by weight of the above (B) hydroxyl group-containing copolymerizable monomer, and 0.35 to 1.0 part by weight of the above (C) a carboxyl group-containing copolymerizable monomer, and 1 to 20 parts by weight of the above (D) polyalkylene glycol mono(meth)acrylate monomer, and containing 0.5 to 5.0 parts by weight based on 100 parts by weight of the above copolymer The above (E) trifunctional or higher isocyanate compound. The adhesive composition according to claim 1, wherein the (B) hydroxyl group-containing comonomer is selected from the group consisting of 8-hydroxyoctyl (meth)acrylate and 6-hydroxyhexyl (meth)acrylate. 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxyl At least one or more of a compound group consisting of a base (meth) acrylamide; and the above (A) (A) alkyl group having a carbon number of C4 to C10 as a (meth) acrylate monomer, B) Among the copolymerizable monomers containing a hydroxyl group, (A) The total amount of at least one or more of 8-hydroxyoctyl acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate is 0 to 0.9 parts by weight. The adhesive composition according to claim 1 or 2, wherein the (C) carboxyl group-containing copolymerizable monomer is selected from the group consisting of (meth)acrylic acid, carboxyethyl (meth) acrylate, and carboxypentyl group. At least one or more of the compound groups consisting of (meth) acrylate. The adhesive composition according to claim 1 or 2, wherein the (D) polyalkylene glycol mono(meth)acrylate monomer is selected from the group consisting of polyalkylene glycol mono(meth)acrylates, At least one or more of the compound group consisting of oxypolyalkylene glycol (meth) acrylate and ethoxylated polyalkylene glycol (meth) acrylate. The adhesive composition according to claim 1 or 2, wherein the (E) trifunctional or higher isocyanate compound is a trimeric isocyanate selected from the group consisting of a hexamethylene diisocyanate compound and an isophorone diisocyanate compound. Addition of trimeric isocyanate, hexamethylene diisocyanate compound, addition of isophorone diisocyanate compound, biuret of hexamethylene diisocyanate compound, isophorone diisocyanate compound At least one or more of the compound groups consisting of biuret bodies. The adhesive composition according to claim 1 or 2, wherein the (H) antistatic agent is contained in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the copolymer, and the melting point is 30 to 80 ° C. An ionic compound, or a copolymer of 0.1 to 5.0% by weight in the above copolymer, having a melting point of 30 to 80 ° C Grade ammonium salt type acrylic monomer. The adhesive composition according to claim 1 or 2, wherein the (I) polyether modified siloxane compound is a polyether modified oxirane compound having an HLB value of 7 to 12; 100 parts by weight of the above copolymer contains 0.01 to 0.5 part by weight of the above (I) polyether modified oxirane compound. The adhesive composition according to claim 1 or 2, wherein the (F) crosslinking inhibitor is contained in an amount of 1.0 to 5.0 parts by weight based on 100 parts by weight of the copolymer. The adhesive composition according to claim 1 or 2, wherein the (G) crosslinking catalyst is an organotin compound, and 0.01 to 0.5 parts by weight of the above (G) is contained with respect to 100 parts by weight of the copolymer. ) Cross-linking catalyst. The adhesive composition according to claim 1 or 2, wherein the adhesive layer obtained by crosslinking the adhesive composition has an adhesive force at a low-speed peeling speed of 0.3 m/min of 0.05 to 0.1 N/25 mm. The adhesive force at a high-speed peeling speed of 30 m/min is 1.0 N/25 mm or less. The adhesive composition according to claim 1 or 2, wherein the adhesive layer obtained by crosslinking the adhesive composition has a surface resistivity of 5.0 × 10 ^{+ 10} Ω / □ or less, and the peeling strip voltage is ±0~1kV. An adhesive film formed by crosslinking an adhesive composition of any one of claims 1 to 11 in a resin film. Face or on both sides. A surface protective film which is obtained by crosslinking an adhesive composition according to any one of claims 1 to 11 on one side of a resin film, via the above adhesive layer On the surface protective film to which the adherend was adhered, it was drawn with a steel ball pen, and then peeled off by the adherend, and no contamination of the adherend occurred. The surface protective film of claim 13 is used as a surface protective film for a polarizing plate. The surface protection film of claim 13, wherein the antistatic and antifouling treatment is performed on a surface of the resin film opposite to the side on which the adhesive layer is formed. The surface protective film of claim 14, wherein the resin film is subjected to an antistatic and antifouling treatment on a surface opposite to the side on which the adhesive layer is formed.