JP2003335829A - Novel copolymer and composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copolymer producing a paint that gives hydrophilicity to the surface of a resin product, metal product, or the like, which remains stable thereon for a prolonged time period, with its coating high in strength. <P>SOLUTION: The copolymer contains repeating units described by general formulas [I], [II], [III] and [IV], and has a number-average molecular weight of 2,000-100,000 in terms of polystyrene as determined by GPC using tetrahydrofuran as the solvent. In the formulas: R<SB>1</SB>is a 1-20C alkyl or aralkyl group; R<SB>2</SB>is a hydrogen aliphatic hydrocarbon group; R<SB>3</SB>is a bivalent group; R<SB>4</SB>is a hydrogen atom or a methyl group; n is a 2-200 integer; R<SB>6</SB>, R<SB>7</SB>and R<SB>8</SB>are each independently a hydrogen atom or a methyl group; X is an ester group having a nonionic hydrophilic group; X is an ester group having a 4-30C alkyl group or a 2-20C fluoroalkyl group; and Z is a functional group having an alkoxysilane. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hydrophilic copolymer, a copolymer composition containing the copolymer, and a coating material containing the copolymer composition. This paint can impart hydrophilicity to resin products, metal products, etc. for a long period of time.

[0002]

2. Description of the Related Art As a method for imparting hydrophilicity to the surface of resin products, metal products, etc., a method of applying a surfactant or the like to the surface is known. Although this method is simple and quick-acting, it has a problem that the surface becomes sticky. Further, since the surfactant is easily peeled off, there is a problem that it lacks in durability.

The inventor

[0004]

[Chemical 6]

[Wherein R ₁ is an alkyl group or aralkyl group having 1 to 20 carbon atoms, R ₂ is a divalent aliphatic hydrocarbon group,
R ₃ is a divalent group shown below

[0006]

[Chemical 7]

(In the formula, R ₅ is a hydrogen atom or a halogen atom, or an alkyl group having 1 to 20 carbon atoms, and m is 1 to 10
Indicates an integer. The carbon atom of the -CONH group is-(CO-R
_2- O-) _n is bonded to the oxygen atom. ), R ₄ is a hydrogen atom or a methyl group, and n is an integer of 2 to 200. ] A copolymer containing a unit represented by the following formula and a unit derived from another vinyl-based monomer has been studied, and some of the results thereof are disclosed in JP-A-4-161415 and JP-A-9-8745.
It is announced in Publication No. 7. And, JP-A-9-8745
No. 7 discloses a unit represented by the above [I], a unit containing a nonionic hydrophilic group, and a unit containing an alkyl group having 4 to 30 carbon atoms or a fluoroalkyl group having 2 to 20 carbon atoms. It was announced that a coating material containing a copolymer with and can impart hydrophilicity to resin products and metal products for a long period of time.

[0008]

[Patent Document 1] Japanese Patent Application Laid-Open No. 9-87457
The coating containing the copolymer described in Japanese Patent Publication is excellent in that it imparts hydrophilicity to resin products and the like for a long time, but it is even more excellent as a coating if the coating film strength can be further increased. It is expected to be good. Therefore, the present invention is one in which the copolymer described in JP-A-9-87457 is modified so that it has excellent coating film strength when formed into a paint and can impart hydrophilicity to the substrate for a long period of time. Is to provide.

[0009]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that the polyester macromonomer and nonionic hydrophilic used in the production of the copolymer described in JP-A-9-87457. A copolymer obtained by copolymerizing a vinyl monomer having a functional group and a vinyl monomer having an alkyl group or a fluoroalkyl group with a vinyl monomer having an alkoxysilane group. Has found that the above problems can be solved, and completed the present invention.

That is, the present invention provides the following general formula [I],
The polystyrene-equivalent number average molecular weight measured by GPC using tetrahydrofuran as a solvent is 2000 to 10 including repeating units represented by [II], [III] and [IV].
Copolymer characterized by being 0000; 0.1 to 50% by weight of said copolymer, and 50 to 9 other film forming resin
A copolymer composition containing 9.9% by weight; a coating material containing the copolymer composition; and a molded article having a layer composed of the copolymer composition.

[0011]

[Chemical 8]

[Wherein R ₁ is an alkyl group or aralkyl group having 1 to 20 carbon atoms, R ₂ is a divalent aliphatic hydrocarbon group,
R ₃ is a divalent group shown below

[0013]

[Chemical 9]

(In the formula, R ₅ is a hydrogen atom or a halogen atom, or an alkyl group having 1 to 20 carbon atoms, and m is 1 to 10
Indicates an integer. The carbon atom of the -CONH group is-(CO-R
_2- O-) _n is bonded to the oxygen atom. ), R ₄ is a hydrogen atom or a methyl group, and n is an integer of 2 to 200. ]

[0015]

[Chemical 10]

(In the formula, R ₆ represents a hydrogen atom or a methyl group, and X represents an ester group having a nonionic hydrophilic group.)

[0017]

[Chemical 11]

(In the formula, R ₇ represents a hydrogen atom or a methyl group, and Y represents an alkyl group having 4 to 30 carbon atoms or 2 to 2 carbon atoms.
An ester group having a fluoroalkyl group of 0 is shown. )

[0019]

[Chemical 12]

(In the formula, R ₈ represents a hydrogen atom or a methyl group, and Z represents a group having an alkoxysilane group.)

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The copolymer according to the present invention comprises a polyester macromonomer represented by the following general formula [IA] and the following general formulas [II-A], [III-A] and [IV −
It is obtained by copolymerizing with a vinyl-based monomer represented by A]. The polyester macromonomer represented by the general formula [IA] may be a mixture of two or more kinds, and similarly, the general formulas [II-A] and [III-
Each vinyl-based monomer represented by A] and [IV-A] may be a mixture of two or more kinds.

[0022]

[Chemical 13]

[0023] [In the formula, R ₅ in _{R 1 ~R 4, R 3,} m,
And n are as defined above. ]

[0024]

[Chemical 14]

(In the formula, R ₆ and X are as defined above.)

[0026]

[Chemical 15]

(In the formula, R ₇ and Y have the same meanings as described above.)

[0028]

[Chemical 16]

(In the formula, R ₈ and Z have the same meanings as described above.) In the general formula [IA], the alkyl group represented by R ₁ is methyl, ethyl, n-propyl or n-butyl. Group, n-
C1-C1 such as pentyl group, n-hexyl group, n-heptyl group, n-octyl group, or 2-ethylhexyl group
0 is preferable. The aralkyl group is preferably one having 7 to 12 carbon atoms such as benzyl group, phenylethyl group, or tolyl group.

As R ₂ , a linear or branched divalent aliphatic hydrocarbon group having 3 to 8 carbon atoms, particularly a divalent aliphatic hydrocarbon group shown below is preferable.

[0031]

[Chemical 17]

As R ₃ ,

[0033]

[Chemical 18]

(Wherein R ₅ has the same meaning as defined above). As R ₄ , when R ₃ is a group having a —CONH— group, a methyl group is preferable. For R ₅ ,
A hydrogen atom is preferred.

As n, 2 to 100, particularly 2 to 50 are preferable. The following are preferred as the polyester macromonomer represented by the general formula [IA].

[0036]

[Chemical 19]

[0037]

[Chemical 20]

(In the formula, R ₄ and n have the same meanings as described above.) The polyester macromonomer represented by the general formula [IA] is described in JP-A-4-161415 or 9-87.
It can be manufactured by the method described in Japanese Patent No. 457. In the general formula [II-A], examples of the nonionic hydrophilic group contained in the ester group represented by X include a hydroxyl group and an ether group. As the ester group, a C2-C10 alkyl ester or aralkyl ester having a hydrophilic group, or a polyethylene glycol ester or a polypropylene glycol ester is preferable. When the ester group is an alkyl group having a hydrophilic group or an aralkyl group, it may further have a halogen atom such as a chlorine atom.

Examples of the vinyl monomer having a nonionic hydrophilic group represented by the general formula [II-A] include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and 3-chloro-2-. Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 3-hydroxy-3-methylbutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 2-hydroxy- Hydroxyalkyl (meth) such as 3-phenoxypropyl (meth) acrylate
Acrylate; having an ether group such as 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate (meth).
Acrylate: (meth) acrylate having a polyether group such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and methoxytriethylene glycol (meth) acrylate. Of these, hydroxyalkyl (meth) acrylate is preferable.

In the general formula [III-A], the ester group represented by Y has an alkyl group having 4 to 30 carbon atoms or a fluoroalkyl group having 2 to 20 carbon atoms, which may be linear or branched. . The alkyl group preferably has 4 to 20 carbon atoms. Examples of the vinyl-based monomer containing an ester group having an alkyl group include n-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate and cyclohexyl ( (Meth) acrylate, n-
Heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, myristyl ( Examples thereof include (meth) acrylates such as (meth) acrylate, isomyristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate.

The fluoroalkyl group may contain other halogen atom such as chlorine atom, amino group, amide group, carbamyl group or sulfonamide group. Examples of the vinyl-based monomer containing an ester group having a fluoroalkyl group include the following fluoroalkyl group-containing (meth) acrylates.

[0042]

[Chemical 21]

The group having an alkoxysilane group in [IV-A] is

[0044]

Embedded image —Si (OR₉)_a(R_Ten)_b (In the formula, R₉And R_TenEach independently has 1 to 4 carbon atoms
Is an alkyl group or an alkoxyalkyl group. a and
b shows the integer of 0-3 which satisfy | fills a + b = 3. R ₉Or
R_TenIf there are multiple R₉Or R_TenIs different
May be. )as well as

[0045]

Embedded image —COO— (CH ₂ ) _c —Si (OR ₁₁ ) _d (R ₁₂ ) _e (wherein R ₁₁ and R ₁₂ are each independently a carbon number of 1 to 4).
Is an alkyl group or an alkoxyalkyl group. c is 1
Is an integer of 3 and d and e are 0 to satisfy d + e = 3.
Indicates an integer of 3. When there are a plurality of R ₁₁ or R ₁₂ , each R ₁₁ or R ₁₂ may be different. ) Is mentioned.

The following groups are preferable as such a group.

[0047]

[Chemical formula 24]

When the vinyl monomer [II-A] having a nonionic hydrophilic group has a hydroxyl group, the alkoxysilane group is bonded to this hydroxyl group in the copolymer and has excellent durability in the coating film. And strength can be imparted. Further, when the film-forming resin forming the copolymer composition contains a hydrolyzable silane group, it can be bonded to the hydrolyzable silane group to further improve the durability and strength of the coating film. .

In addition to the repeating units represented by the general formulas [I] to [IV], the copolymer may contain repeating units derived from other copolymerizable vinyl monomers. Such vinyl monomers include styrenes, vinyl esters, vinyl ethers, vinyl thioethers,
Examples include (meth) acrylates other than those represented by the general formula [III-A] and other vinyl compounds. These may be used in combination of two or more.

Examples of styrenes include styrene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-tert-butoxystyrene, p-chloromethylstyrene, p-acetoxystyrene, and divinylbenzene. . Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl cinnamate, and vinyl methacrylate.

Examples of vinyl ethers include ethyl vinyl ether, n-propyl vinyl ether, butyl vinyl ether, ethylene glycol monovinyl ether, butanediol divinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether,
4,4-bis (vinyloxyethyloxy) biphenyl,
And 1,4-bis (vinyloxyethyloxy) benzene and the like.

Vinyl thioethers include 4,4-
Bis (vinyloxyethyloxy) diphenyl sulfide, 4,4-bis (vinyloxyethyloxy) diphenyl sulfone, ethyl vinyl sulfide, n-propyl vinyl sulfide, cyclohexyl vinyl sulfide, ethylene glycol monovinyl sulfide, ethylene glycol divinyl sulfide, diethylene glycol divinyl Examples thereof include sulfide and phenyl vinyl sulfide.

The (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, benzyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid , 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, and 2
-(Meth) acryloyloxyethyl acid phosphate and the like.

Other vinyl compounds include vinyl compounds such as indene, N-vinylpyrrolidone, N-acryloylmorpholine, N-vinylcaprolactam, N-vinylpiperidine, N-vinylformamide, and vinylnorbornene. The copolymer according to the present invention includes a polyester macromonomer represented by the general formula [IA], general formulas [II-A], [III-A], and [IV-A].
Can be produced by copolymerizing the vinyl-based monomer represented by and another vinyl-based monomer that can be copolymerized, if desired, in the presence of a radical initiator.

The repeating unit derived from the polyester macromonomer [IA] accounts for 5% by weight or more, particularly 5 to 20% by weight of the whole copolymer. The repeating unit derived from the vinyl-based monomer [II-A] having a nonionic hydrophilic group is 40 to 90% by weight, especially 50% by weight of the whole copolymer.
It is preferable to make up 80% by weight. When the repeating unit derived from [II-A] is less than 40% by weight, a copolymer having excellent hydrophilicity cannot be obtained, and when it exceeds 90% by weight, the copolymer has other film forming properties. When formulated into a coating composition, the compatibility with other resins becomes poor.

The repeating unit derived from the vinyl-based monomer [III-A] having an alkyl group or a fluoroalkyl group is
2 to 60% by weight of the whole copolymer, especially 10 to 40% by weight
Preferably occupy The hydrophilicity of the copolymer is greatly influenced by the ratio of the vinyl-based monomer [II-A] contributing to hydrophilicity and the vinyl-based monomer [III-A] contributing to hydrophobicity. Therefore, [II-A] and [III-A]
The repeating unit derived from is usually 98: 2 by weight ratio.
It is preferably used in the range of 60:40, particularly 95: 5 to 80:20. If the ratio of the repeating units derived from [III-A] is less than 2 or more than 40, a copolymer having desired hydrophilicity cannot be obtained.

The repeating unit derived from the vinyl monomer [IV-A] having an alkoxysilane group is 1 unit of the whole copolymer.
It is preferable to occupy 40 to 40% by weight, particularly 2 to 20% by weight. The repeating unit derived from another copolymerizable vinyl-based monomer preferably accounts for 0 to 50% by weight, and particularly 0 to 40% by weight of the entire copolymer. The reaction is carried out by appropriately selecting the polymerization conditions such as the type and amount of the radical initiator, the polymerization temperature, the type of the solvent, the monomer concentration during the polymerization reaction, and the method of supplying the monomer to the polymerization system. The polymer has a polystyrene reduced number average molecular weight of 20 by GPC (gel permeation chromatography) using tetrahydrofuran as a solvent.
It is performed so that it becomes 00-100,000. Molecular weight is 300
It is preferable to carry out so as to be 0 to 50,000. When the molecular weight of the copolymer is less than 2000, the copolymer is likely to bleed out from the coating film containing the copolymer, and the hydrophilic property is deteriorated with time. Molecular weight is 1
If it exceeds 00000, the compatibility with other film-forming resins will decrease when the copolymer is used as a coating material.

The copolymer obtained as described above is combined with another film-forming resin to prepare a copolymer composition used in a coating composition. As the film-forming resin, any resin used for paints such as thermoplastic resins, thermosetting resins, and UV-curable resins can be used, and the characteristics required for the base material to which the paint is applied and the coating film, etc. It may be appropriately selected according to

As the thermoplastic resin, polyvinyl chloride,
Examples thereof include polystyrene, polystyrene-acrylonitrile copolymer, polyester, polyamide, polyacrylic acid ester, and polyurethane. Examples of the thermosetting resin include polyurethane, epoxy resin, oxetane resin, and unsaturated polyester resin. In the case of polyurethane, the copolymer according to the present invention is mixed with the polyols that are commonly used in the production of polyurethane, and after further mixing the isocyanate compound and the curing catalyst, the coating is applied to the substrate and cured to form a coating film. Can be formed. When a thermosetting resin is used as the film-forming resin, the resulting coating film has high strength and chemical resistance.

Examples of the UV curable resin include monofunctional monomers such as butyl acrylate, tetrahydrofurfuryl acrylate and vinylpyrrolidone; and polyfunctional oligomers such as polyurethane acrylate and polyester acrylate. A coating film showing good surface properties and high strength in a short time is formed by mixing an ultraviolet curable resin and the copolymer according to the present invention, applying the same on a substrate, and then irradiating it with ultraviolet rays by a conventional method. Can be made.

One of the preferred film-forming resins is one having a hydrolyzable silane group. Examples of such a resin include vinyltrimethoxysilane or γ-
A copolymer containing a repeating unit derived from methacryloxypropyltrimethoxysilane, the above-mentioned thermoplastic resin,
Examples thereof include a thermosetting resin or an ultraviolet curable resin containing a hydrolyzable silane group. When a resin having a hydrolyzable silane group is used, the hydrolyzable silane group is bonded to the alkoxysilane group in the copolymer, so that a coating film having high strength, chemical resistance, and fast-acting property can be formed. You can

The blending amount of the copolymer in the total amount of the copolymer according to the present invention and the film-forming resin is usually 0.1 to 50.
% By weight, preferably 0.5-40% by weight. If the content of the copolymer is less than 0.1% by weight, sufficient hydrophilicity cannot be obtained, and if it exceeds 50% by weight, cracks and wrinkles may occur in the coating film. The copolymer composition of this copolymer and a film-forming resin is dissolved in a conventional solvent, and if desired, a conventional auxiliary agent is further added to obtain a coating, which is used as a base for resins, metals, wood, building materials, etc. By coating the surface of the material, a hydrophilic layer having high durability can be formed on the surface of the base material. Examples of the coating method include a spray method, a bar coating method, a roll coating method, a spin coating method, and a dipping method. The coating film preferably has a thickness of 0.1 to 200 μm, particularly 0.1 to 50 μm after drying. When the thickness of the coating film is less than 0.1 μm, the hydrophilicity is inferior, and when it exceeds 200 μm, the cost becomes high, which is not preferable.

The resin used as the base material is polyethylene,
Polyolefin resin such as polypropylene, polystyrene resin, polystyrene-acrylonitrile copolymer resin, A
Examples thereof include BS resin, polyester resin, polyamide resin, polyacrylic acid ester resin, and polyurethane resin. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, and polycarbonate. As a polyamide resin,
Examples thereof include thermoplastic resins such as nylon 6, nylon 6-6, nylon 6-10, nylon 11, and nylon 12, and thermosetting resins such as epoxy resin, phenol resin, urea resin, and melamine resin. Further, those containing the above-mentioned hydrolyzable silane group in these resins are also preferable as the base material.

Examples of the metal substrate include iron, aluminum, zinc, copper and the like.

[0065]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples unless it exceeds the gist thereof. The evaluation of hydrophilicity is
It was carried out by measuring the value of receding contact angle at 23 ° C. by the Wilhelmy method using Orientec DCA-20. [Production Example 1] (Production of Polyester Alcohol) A colorless and transparent polyester alcohol was produced from 2-ethylhexanol and ε-caprolactone by the method described in Reference Example C of JP-A-9-87457. The hydroxyl value of the obtained polyester alcohol is 5
6.78KOHmg / g, acid value is 0.50KOHmg
/ G. [Production Example 2] (Production of polyester macromonomer) By the method described in Reference Example D of JP-A-9-87457, the polyester alcohol of Production Example 1 and m-isopropenyl-α, α-dimethylbenzyl isocyanate are prepared. And were reacted to produce a polyester macromonomer. [Production Example 3] (Production of Composite Resin Having Hydrolyzable Silane Group) (i) In a flask equipped with a silicate oligomer stirring blade, a reflux condenser and a thermometer, 234 g of tetramethoxysilane and 74 g of methanol were mixed. Then, 22.2 g of 0.05% hydrochloric acid was added, and the mixture was stirred at a liquid temperature of 65 ° C for 2 hours. Then replace the reflux condenser with an extraction tube,
The liquid temperature was raised to 150 ° C. to distill off methanol. Further, it was kept at 150 ° C. for 3 hours to obtain a silicate oligomer having a hydrolyzable silane group. The degree of polymerization of the obtained silicate oligomer was 3 to 6, and the number of hydroxy groups in one molecule was 10 or more. (Ii) In a flask equipped with an acrylic alcohol-soluble resin stirring blade, a reflux condenser, a thermometer, and a nitrogen introducing tube, a mixed liquid of 51 g of methyl ethyl ketone and 61 g of isopropyl alcohol, 28 g of methyl methacrylate,
10 g of butyl acrylate and 2 g of 2-hydroxyethyl acrylate were added, and the mixture was stirred at room temperature. The reaction solution is 65
After the temperature was raised to 0 ° C., a solution of 0.61 g of 2,2′-azobisisobutyronitrile in 5 g of methyl ethyl ketone was added dropwise,
The mixture was stirred at 65 ° C for 7 hours. The solvent was distilled off at room temperature using an evaporator, followed by drying under reduced pressure at 65 ° C. to obtain an acrylic alcohol-soluble resin. (Iii) To a flask equipped with a composite resin stirring blade having a hydrolyzable silane, a reflux condenser, a thermometer, and a nitrogen introduction tube, a solution of 5 g of the acrylic alcohol-soluble resin (ii) in 15 g of ethanol was added, and the mixture was heated at 65 ° C. 5 g of silicate oligomer (i) was added. Next, 0.95 g of 1N hydrochloric acid was added to the reaction solution and stirred at 65 ° C. for 30 minutes to obtain a composite resin having a hydrolyzable silane group. [Example 1] In a flask equipped with a stirring blade, a reflux condenser, and a gas introduction port, the polyester macromonomer of Production Example 2; 3.53 g polyethylene glycol methacrylate; 23.65 g (PME400 manufactured by NOF Corporation) 4- Hydroxybutyl acrylate; 1.77 g Heptadecafluorodecyl acrylate; 2.82 g (Osaka Organic Chemical Industry Co., Ltd. biscot 17F) γ-methacryloxypropyltrimethoxysilane; 3.53 g (Shin-Etsu Chemical Co., Ltd. KBM503) ) T-Butylpa-oxyisopropyl carbonate; 0.29 g (Perbutyl I manufactured by NOF CORPORATION) n-dodecanethiol; 0.33 g methyl isobutyl ketone; 82.37 g was charged, and under a nitrogen stream at 110 ° C. for 8 hours. A polymerization reaction was carried out. The reaction solution was poured into hexane, and the precipitated copolymer was collected and dried. The yield was 88%. Also,
The polystyrene reduced number average molecular weight measured by GPC using tetrahydrofuran as a solvent was 12,000.

0.1 g of the obtained copolymer was dissolved in 1 g of methyl ethyl ketone and mixed with 200 g of a solution of 50 g of the resin containing the composite resin having a hydrolyzable silane group obtained in Production Example 3 in 200 g of methyl ethyl ketone to prepare a coating material. did. A polyethylene terephthalate film (1
(6 mm × 50 mm × 0.2 mm) was dipped and pulled up, and then dried at 70 ° C. for 2 hours to form a coating film having a thickness of 8 μm.

The receding contact angle of the obtained coating film was 0 degree,
This value did not change even when immersed in warm water of 40 ° C. for 300 hours. The pencil hardness of this coating film was 2H. [Example 2] In a flask equipped with a stirring blade, a reflux condenser, and a gas inlet, the polyester macromonomer synthesized in Production Example 2; 3.44 g polyethylene glycol methacrylate; 17.20 g (PME400 manufactured by NOF CORPORATION). 4-hydroxybutyl acrylate; 1.72g heptadecafluorodecyl acrylate 2.75g (Osaka Organic Chemical Industry Co., Ltd. VISCORT 17F) isobornyl methacrylate; 7.57g γ-methacryloxypropyltrimethoxysilane; 72 g (KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.) t-butylperoxypropyl carbonate; 1.35 g (Perbutyl I manufactured by NOF Corporation) n-dodecanethiol; 1.55 g methyl isobutyl ketone; 80.27 g were charged, and nitrogen was added. 110 ° C under air flow 8 hours to polymerization.
After the polymerization, the reaction solution was put into hexane, and the precipitated copolymer was collected and dried. The yield was 90%. G of the copolymer obtained here using tetrahydrofuran as a solvent
The polystyrene equivalent number average molecular weight measured by PC is 550.
It was 0.

0.1 g of the obtained copolymer was dissolved in 1 g of methyl ethyl ketone, and the solution was added to 200 g of a solution of 50 g of the resin containing the composite resin having a hydrolyzable silane group obtained in Production Example 3 in 200 g of methyl ethyl ketone. did. A polyethylene terephthalate film was dipped in the obtained coating material, pulled up, and then dried at 70 ° C. for 2 hours to form a coating film having a thickness of 8 μm.

The receding contact angle of the obtained coating film was 10 degrees, and it was 0 degrees when immersed in 40 ° C. hot water for 300 hours. The pencil hardness of this coating film was 2H. [Example 3] In a flask equipped with a stirring blade, a reflux condenser, and a gas inlet, the polyester macromonomer synthesized in Production Example 2; 3.26 g polyethylene glycol methacrylate; 16.30 g (PME400 manufactured by NOF CORPORATION). 4-hydroxybutyl acrylate; 1.63 g heptadecafluorodecyl acrylate; 2.61 g (Viscoat 17F manufactured by Osaka Organic Chemical Industry Co., Ltd.) methyl methacrylate; 7.17 g γ-methacryloxypropyltrimethoxysilane; 1.63 g (Shin-Etsu Chemical Co., Ltd. KBM503) t-Butylpa-oxyisopropyl carbonate; 0.46 (Nippon Oil & Fat Co., Ltd. Perbutyl I) n-dodecanethiol; 0.53 g Methyl isobutyl ketone; 76.07 g were charged, and under a nitrogen stream. 8 hours at 110 ° C Polymerized.
After the polymerization, the reaction solution was put into hexane, and the precipitated copolymer was collected and dried. The yield was 89%. G of the copolymer obtained here using tetrahydrofuran as a solvent
The polystyrene equivalent number average molecular weight measured by PC is 110.
It was 00.

0.1 g of the obtained copolymer was dissolved in 1 g of methyl ethyl ketone and added to 200 g of a solution of 50 g of the resin containing the composite resin having a hydrolyzable silane group obtained in Production Example 3 in 200 g of methyl ethyl ketone to prepare a paint. did. A polyethylene terephthalate film was dipped in the obtained coating material, pulled up, and then dried at 70 ° C. for 2 hours to form a coating film having a thickness of 8 μm.

The receding contact angle of the obtained coating film was 25 degrees, and it was 15 degrees when immersed in 40 ° C. hot water for 300 hours. The pencil hardness of this coating film was H. [Comparative Example 1] In a flask equipped with a stirring blade, a reflux condenser, and a gas inlet, the polyester macromonomer synthesized in Production Example 2; 12.81 g polyethylene glycol methacrylate; 24.08 g (PME400 manufactured by NOF CORPORATION). 4-Hydroxybutyl acrylate; 6.99 g t-Butylpa-oxyisopropyl carbonate; 1.51 g (Perbutyl I manufactured by NOF CORPORATION) n-dodecanethiol; 1.17 g Methyl isobutyl ketone; 102.4 g, and nitrogen stream Polymerization under 110 ° C. for 8 hours.
After the polymerization, the reaction solution was put into hexane, and the precipitated copolymer was collected and dried. The yield was 85%. G of the copolymer obtained here using tetrahydrofuran as a solvent
The polystyrene equivalent number average molecular weight measured by PC is 870.
It was 0.

0.1 g of the obtained copolymer was dissolved in 1 g of methyl ethyl ketone and added to 200 g of methyl ethyl ketone resin solution containing 50 g of the resin containing the composite resin having a hydrolyzable silane group obtained in Production Example 3 to prepare a paint. did. A polyethylene terephthalate film was dipped in the obtained coating material, pulled up, and then dried at 70 ° C. for 2 hours to form a coating film having a thickness of 8 μm.

The receding contact angle of the obtained coating film was 23 degrees, but the variation among the samples was large. When it was immersed in warm water of 40 ° C. for 300 hours, it became 50 degrees. The pencil hardness of this coating film was B. [Comparative Example 2] In a flask equipped with a stirring blade, a reflux condenser, and a gas inlet, the polyester macromonomer synthesized in Production Example 2; 3.31 g polyethylene glycol methacrylate; 19.86 g (PME400 manufactured by NOF CORPORATION). 4-hydroxybutyl acrylate; 1.66 g heptadecafluorodecyl acrylate; 2.65 g (Viscoat 17F manufactured by Osaka Organic Chemical Industry Co., Ltd.) Methyl methacrylate; 5.63 g t-butylperoxyisopropyl carbonate; 1.63 g (NOF Corporation) Perbutyl I) n-dodecanethiol; 1.87 g methyl isobutyl ketone; 77.26 g were charged and polymerized at 110 ° C. for 8 hours under a nitrogen stream.
After the polymerization, the reaction solution was put into hexane, and the precipitated copolymer was collected and dried. The yield was 89%. G of the copolymer obtained here using tetrahydrofuran as a solvent
The polystyrene equivalent number average molecular weight measured by PC is 110.
It was 00.

0.1 g of the obtained copolymer was dissolved in 1 g of methyl ethyl ketone and added to 200 g of a solution of 50 g of the resin containing the composite resin having a hydrolyzable silane group obtained in Production Example 3 in 200 g of methyl ethyl ketone. did. A polyethylene terephthalate film was dipped in the obtained coating material, pulled up, and then dried at 70 ° C. for 2 hours to form a coating film having a thickness of 8 μm.

The receding contact angle of the obtained coating film was 25 degrees, and it was 15 degrees when immersed in 40 ° C. hot water for 300 hours. The pencil hardness of this coating film was H.

[0076]

EFFECT OF THE INVENTION The copolymer according to the present invention is excellent in hydrophilicity and has high compatibility with various resins, so that it is suitable for producing a copolymer composition for forming a coating film which requires durability. Can be used. Further, the copolymer composition produced from this copolymer and various resins, by dissolving in a solvent, various plastics, by applying to a molded article made of metal,
A coating film having excellent hydrophilicity, strength and adhesion can be easily formed. The formed coating film does not lose its hydrophilicity even by wiping with water. Therefore, when it is used in products that require hydrophilicity such as various film products and coating materials for building materials, it is possible to impart stable hydrophilicity over a long period of time.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 183/04 C09D 183/04 // (C08L 101/00 C08L 55:00 55:00) F term (reference) ) 4J002 AA011 AA021 BC031 BC061 BD041 BG021 BQ001 BQ002 CD001 CF001 CF211 CK001 CL001 FD201 GH02 4J027 AB01 AB03 AJ01 AJ02 BA02 BA04 BA07 BA08 BA09 DL101 NA102 CH02 CH01 CH02 CH02 CH04 CH2 CH041 CH2 CH041 CH021 CH031 CH021

Claims (5)

[Claims] 1. A polystyrene-equivalent number average molecular weight measured by GPC using tetrahydrofuran as a solvent, which comprises repeating units represented by the following general formulas [I], [II], [III] and [IV]. A copolymer characterized by being: [Chemical 1] [Wherein R ₁ is an alkyl group or aralkyl group having 1 to 20 carbon atoms, R ₂ is a divalent aliphatic hydrocarbon group, and R ₃ is (In the formula, R ₅ is a hydrogen atom or a halogen atom, or an alkyl group having 1 to 20 carbon atoms, m is an integer of 1 to 10. The carbon atom of the —CONH group is — (CO—R ₂ —O—). _n
-Bonds to the oxygen atom of. ), R ₄ is a hydrogen atom or a methyl group, and n is an integer of 2 to 200. ] [Chemical 3] (In the formula, R ₆ represents a hydrogen atom or a methyl group, and X represents an ester group having a nonionic hydrophilic group.) (In the formula, R ₇ represents a hydrogen atom or a methyl group, and Y represents an alkyl group having 4 to 30 carbon atoms or an ester group having a fluoroalkyl group having 2 to 20 carbon atoms.) (In the formula, R ₈ represents a hydrogen atom or a methyl group, and Z represents a group having an alkoxysilane group.) 2. The repeating unit represented by the general formula [I] is 5 to 20% by weight, and the repeating unit represented by [II] is 40% by weight.
-80% by weight, 5 to 5% of the repeating unit represented by [III]
50% by weight, and 1 to the repeating unit represented by [IV]
The copolymer according to claim 1, wherein the copolymer is contained at 40% by weight. 3. The copolymer according to claim 1 or 2
A copolymer composition comprising 50% by weight and 50 to 99.9% by weight of another film-forming resin. 4. A coating material comprising the copolymer composition according to claim 3. 5. A molded article having a layer made of the copolymer composition according to claim 3.