KR101265398B1 - Water-based metal-surface-treating agent - Google Patents

Abstract

［식 중, R1 은 수소 원자 또는 메틸기를 나타내고, R2 는 일반식 (II)

(식 중, R3, R4 및 R5 는 서로 독립적으로, 수소 원자, 수산기 또는 탄소수 1 ∼ 3 의 알킬기를 나타낸다) 로 나타내는 기를 나타낸다］로 나타내는 (메트)아크릴산에스테르 (A) 로부터의 중합 단위를 분자 중에 갖는 중합체로서 유리 전이 온도가 0 ∼ 70 ℃ 인 중합체 (P), 유화제 및 물을 함유하고, 중합체 (P) 가 그 유화제에 의해 분산되어 있는 금속 표면 처리제. 본 처리제는 저장 안정성이 우수하며, 내자외선 열화성, 내알칼리성, 내산성, 가공성 및 피막 투과성이 우수한 피막을 형성할 수 있다.The compound of formula (I)

[Wherein, R1 represents a hydrogen atom or a methyl group, and R2 represents a general formula (II)

The polymer unit from the (meth) acrylic acid ester (A) represented by (wherein R <3>, R <4> and R <5> represents a hydrogen atom, a hydroxyl group, or a C1-C3 alkyl group independently of each other) is shown in the molecule | numerator. The metal surface treating agent which contains the polymer (P), emulsifier, and water whose glass transition temperature is 0-70 degreeC as a polymer to have, and the polymer (P) is disperse | distributed with the emulsifier. This treatment agent is excellent in storage stability and can form a film excellent in ultraviolet ray deterioration resistance, alkali resistance, acid resistance, processability and film permeability.

Description

WATER-BASED METAL-SURFACE-TREATING AGENT}

The present invention relates to an aqueous metal surface treatment agent which is excellent in storage stability and capable of forming a film having excellent UV resistance, alkali resistance, acid resistance, processability, and film transparency.

Generally, it is excellent in adhesiveness to the surface of a metal material and gives a corrosion resistance, workability, etc. to the surface of a metal material, The resin chromate by the processing liquid which contains organic resin, chromic acid, dichromic acid, or their salt as a main component in a metal material surface. Although the method of performing a process was common, the environment-adaptive non-chromate organic resin film process etc. which replaced chromium by another crosslinkable metal are currently provided for practical use.

As a non-chromate organic resin film processing technique, patent document 1 manufactures the highly weather-resistant emulsion characterized by emulsion-polymerizing the monomer composition containing at least (meth) acrylic acid ester, a dialkyl (meth) acrylamide, and surfactant. A method is disclosed.

As the non-chromate organic resin film treatment technology, Patent Document 2 further emulsifies the monomer composition containing at least (meth) acrylic acid ester, 0.1 to 20% by mass of styrene and a surfactant to the (meth) acrylic acid ester. A method for producing a particulate emulsion characterized by polymerizing is disclosed.

As a non-chromate organic resin film technique, Patent Document 3 further describes (A) an aqueous resin having a carboxyl group and an acid amide bond, (B) Al, Mg, Ca, Zn, Ni, Co, Fe, Zr, Ti, Disclosed is a surface treatment agent for metal plate material which does not contain chromium, characterized by containing one or two or more metal compounds selected from metal compounds of V, W, Mn and Ce, and (C) a silicon compound.

As a non-chromate organic resin film technique, patent document 4 contains 0.1-30 mass% of specific nitrogen containing radically polymerizable unsaturated monomer (a) and 1-20 mass% of carboxyl groups with respect to the sum total of the monomer which comprises it. Of the resin component (A) obtained by radical polymerization reaction of the monomer mixture containing a radically polymerizable unsaturated monomer (b) and 50-98.9 mass% of other radically polymerizable unsaturated monomer (c), and the resin component (A) The aqueous coating material containing 0.01-10 mass parts of organic acid catalysts (C) is disclosed with respect to 100 mass parts of solid content.

Japanese Unexamined Patent Publication No. 2000-327704 Japanese Unexamined Patent Publication No. 2000-327722 Japanese Laid-Open Patent Publication 2003-201579 Japanese Laid-Open Patent Publication 2006-152056

However, any of the above-described methods and surface treatment agents have the performance of being used as a substitute for the resin chromate coating, have excellent storage stability, and can form a coating having excellent ultraviolet ray deterioration resistance, alkali resistance, acid resistance, processability and coating transparency. It is difficult to say that it is possible, and development of the surface treating agent and the processing method which can satisfy | fill these comprehensively is strongly desired.

An object of the present invention is to solve the above problems with the prior art, and to provide an aqueous surface treatment agent which is excellent in storage stability and can form a film having excellent UV resistance, alkali resistance, acid resistance, processability and film transparency. It is.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve these problems, As a result, the polymer which has a polymerization unit from the (meth) acrylic acid ester which has a specific structure in a molecule | numerator, and has a polymer with a glass transition temperature of 0-70 degreeC, and an emulsifier, The aqueous surface treating agent contained was found to be excellent in storage stability and to form a film excellent in ultraviolet ray deterioration resistance, alkali resistance, acid resistance, processability, and film transparency, thus completing the present invention.

That is, the present invention is of general formula (I)

[Formula 1]

[Wherein, R 1 represents a hydrogen atom or a methyl group, and R 2 represents general formula (II)

[Formula 2]

(In the formula, R3, R4 and R5 independently represent a group represented by a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms.) The polymerization unit from (meth) acrylic acid ester (A) represented by It is related with the metal surface treating agent which contains the polymer (P), emulsifier, and water whose glass transition temperature is 0-70 degreeC as a polymer to have, and the polymer (P) is disperse | distributed with the emulsifier.

,β-에틸렌성 불포화 카르복실산 (C) 로부터의 중합 단위」및「반응성 유화제로부터의 중합 단위」에 대해서도 동일하게 적용된다.In addition, "the polymerization unit from (meth) acrylic acid ester (A)" shall mean the polymerization unit in which the carbon-carbon double bond in (meth) acrylic acid ester (A) is opened, and this is continued and described as " Polymerized Unit from Silicon-Containing Monomer (B) ","

The same applies to "polymerized unit from (beta) -ethylenically unsaturated carboxylic acid (C)" and "polymerized unit from reactive emulsifier".

Polymer (P) is of the general formula (III)

(3)

[In formula, R <6>, R <7> and R <8> represent a hydrogen atom, a hydroxyl group, a C1-C3 alkyl group, a C1-C3 alkoxy group, or a C1-C3 alkoxyl alkoxy group independently of each other, X is the formula (IV)

[Formula 4]

Or general formula (V)

[Chemical Formula 5]

(In formula, R <9> represents a hydrogen atom or a methyl group, R <10> represents a group represented by a C1-C12 alkylene group.) It is preferable to have a polymerization unit from the silicon-containing monomer (B) shown in a molecule | numerator.

,β-에틸렌성 불포화 카르복실산 (C) 로부터의 중합 단위를 분자 중에 갖는 것이 바람직하다.The polymer (P) is also

It is preferable to have a polymerization unit from, (beta) -ethylenically unsaturated carboxylic acid (C) in a molecule | numerator.

It is preferable that the ratio of the polymerization unit from (meth) acrylic acid ester (A) is 0.1-50 mass parts with respect to 100 mass parts of polymers (P).

It is preferable that the ratio of the polymerization unit from a silicon-containing monomer (B) is 0.5-2.0 mass parts with respect to 100 mass parts of polymers (P).

It is preferable that the acid value of a polymer (P) is 5-40 mgKOH / g.

It is preferable that the said metal surface treating agent contains 0.5-50 mass parts of plasticizers (Q) with respect to 100 mass parts of polymers (P).

The plasticizer (Q) preferably has at least one ester bond and / or at least one ether bond in the molecule, and 2,2,4-trimethyl-1,3pentanediol monoisobutylate, diethylene glycol monobutyl ether It is more preferable that it is at least 1 sort (s) chosen from acetate, ethylene glycol monobutyl ether, and dipropylene glycol n-butyl ether.

By using the water-based metal surface treatment agent excellent in storage stability of the present invention, a film excellent in ultraviolet ray deterioration resistance, alkali resistance, acid resistance, processability and film transparency can be formed.

The water-based metal surface treatment agent of the present invention is of general formula (I)

[Formula 6]

[Wherein, R 1 represents a hydrogen atom or a methyl group, and R 2 represents general formula (II)

[Formula 7]

(In the formula, R3, R4 and R5 independently represent a group represented by a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms.) The polymerization unit from (meth) acrylic acid ester (A) represented by It is necessary to contain the polymer (P) whose glass transition temperature is 0-70 degreeC as a polymer which has.

The glass transition temperature of the polymer (P) needs to be 0-70 degreeC, and can maintain favorable alkali resistance, acid resistance, workability, and film transparency by this. From the said viewpoint, it is preferable that it is 10-60 degreeC, and, as for the glass transition temperature, it is more preferable that it is 20-50 degreeC. When glass transition temperature is less than 0 degreeC, not only alkali resistance and acid resistance fall remarkably, but the film hardness required at the time of processing cannot be obtained. On the contrary, when it exceeds 70 degreeC, storage stability and the film followability required at the time of processing will fall remarkably.

The effect which a (meth) acrylic acid ester (A) unit gives to a polymer (P) is the improvement of alkali resistance, acid resistance, and workability with a raise of glass transition temperature.

Moreover, R2 of (meth) acrylic acid ester (A) needs to be formed only by a saturated bond. When an unsaturated bond is provided, radical reaction will generate | occur | produce by ultraviolet-ray, and a chromophore or a chromophore is formed, and ultraviolet-ray deterioration remarkably falls.

Regarding the definitions of R 3, R 4 and R 5 in the general formula (II), the alkyl group having 1 to 3 carbon atoms includes a methyl group, an ethyl group, a propyl group and an isopropyl group.

Although it does not specifically limit as (meth) acrylic acid ester (A), Boryl acrylate, isobornyl acrylate, bornyl methacrylate, isobornyl methacrylate, etc. are mentioned.

Polymer (P) contained in the water-based metal surface treatment agent of the present invention is represented by the general formula (III)

[Formula 8]

[In formula, R <6>, R <7> and R <8> represent a hydrogen atom, a hydroxyl group, a C1-C3 alkyl group, a C1-C3 alkoxy group, or a C1-C3 alkoxy C1-C3 alkoxy group each independently, and X is Formula (IV)

[Chemical Formula 9]

Or general formula (V)

[Formula 10]

It is preferable to have a polymerization unit from the silicon-containing monomer (B) represented by (wherein R9 represents a hydrogen atom or a methyl group and R10 represents a C1-12 alkylene group). As a result, adhesion to the surface of the metal to be treated is enhanced, and thus workability is improved, and alkali resistance and acid resistance are improved.

Regarding the definitions of R6, R7 and R8 in the general formula (III), the alkyl group having 1 to 3 carbon atoms includes a methyl group, an ethyl group, a propyl group and an isopropyl group, and the alkoxy group having 1 to 3 carbon atoms is a methoxy group, an ethoxy group or a pro An alkoxy group and an isopropoxy group are included, and a C1-C3 alkoxy C1-C3 alkoxy group contains a methoxyethoxy group etc.

It is preferable that R <10> in general formula (V) is a C1-C6 alkylene group, and it is more preferable that it is a C1-C4 alkylene group.

Regarding the definition of R10 in General Formula (V), as the alkylene group, a methylene group, an ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, octamethylene group, decamethylene group, dodecamethylene group Etc. can be mentioned.

Although it does not specifically limit as a silicon containing monomer (B), Vinyl trimethoxysilane, vinyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldimethoxysilane, 3-metha Krilloxy propyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, etc. are mentioned.

,β-에틸렌성 불포화 카르복실산 (C) 로부터의 중합 단위를 분자 중에 갖는 것이 바람직하고, 그것에 의해, 피처리 금속 표면과의 밀착이 보다 강고해져, 내산성 및 가공성이 향상된다. The polymer (P) is also

It is preferable to have a polymerized unit from a (beta) -ethylenically unsaturated carboxylic acid (C) in a molecule | numerator, and adhesiveness with the to-be-processed metal surface becomes stronger by this, and acid resistance and workability improve.

,β-에틸렌성 불포화 카르복실산 (C) 로는, 특별히 한정되는 것은 아니지만, 아크릴산, 메타크릴산, 말레산, 이타콘산, 푸마르산, 크로톤산 등을 들 수 있다.

Although it does not specifically limit as, (beta) -ethylenically unsaturated carboxylic acid (C), Acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, a crotonic acid, etc. are mentioned.

About the compounding quantity of (meth) acrylic acid ester (A), it is preferable that the ratio of the polymer unit from (meth) acrylic acid ester (A) is 0.1-50 mass parts with respect to 100 mass parts of polymers (P), and is 0.5-45 It is more preferable that it is mass part, and it is still more preferable that it is 3.0-35 mass part. When the said ratio is less than 0.1 mass part with respect to 100 mass parts of polymers (P), the addition effect of (meth) acrylic acid ester (A) will become difficult to express, and when it exceeds 50 mass parts, it will become difficult to maintain storage stability.

Regarding the blending amount of the silicon-containing monomer (B), the ratio of the polymer unit from the silicon-containing monomer (B) is preferably 0.5 to 2.0 parts by mass, more preferably 0.7 to 2.0 parts by mass with respect to 100 parts by mass of the polymer (P). It is preferable and it is still more preferable that it is 1.0-2.0 mass parts. When the said ratio is less than 0.5 mass part with respect to 100 mass parts of polymers (P), the addition effect of a silicon-containing monomer (B) becomes difficult to express, and when it exceeds 2.0 mass part, there exists a tendency for storage stability to fall.

,β-에틸렌성 불포화 카르복실산 (C) 의 배합량에 관하여, (C) 로부터의 중합체 단위에서 유래되는 중합체 (P) 의 산가가 5 ∼ 40 mgKOH/g 인 것이 바람직하고, 10 ∼ 35 mgKOH/g 인 것이 보다 바람직하고, 15 ∼ 30 mgKOH/g 인 것이 한층 더 바람직하다. 산가가 5 mgKOH/g 미만이면,

,β-에틸렌성 불포화 카르복실산 (C) 의 첨가 효과가 발현하기 어려워진다. 반대로 40 mgKOH/g 를 초과하면, 중합체 (P) 의 수용성이 강해져, 저장 안정성이 저하될 뿐만 아니라, 내알칼리성 및 내산성이 저하되는 경향이 된다.

About the compounding quantity of (beta) -ethylenically unsaturated carboxylic acid (C), it is preferable that the acid value of the polymer (P) derived from the polymer unit from (C) is 5-40 mgKOH / g, and it is 10-35 mgKOH / It is more preferable that it is g, and it is further more preferable that it is 15-30 mgKOH / g. If the acid value is less than 5 mgKOH / g,

The addition effect of the (beta) -ethylenically unsaturated carboxylic acid (C) becomes difficult to express. On the contrary, when it exceeds 40 mgKOH / g, the water solubility of the polymer (P) becomes strong, storage stability falls, and there exists a tendency for alkali resistance and acid resistance to fall.

When using a reactive emulsifier as an emulsifier used at the time of manufacture of a polymer (P), the polymer unit from a reactive emulsifier also becomes a structural component of a polymer (P). When using only a reactive emulsifier as an emulsifier, it is preferable that it is 0.5-5 mass parts with respect to 100 mass parts of polymers (P), and, as for the ratio of the polymer unit from a reactive emulsifier, it is more preferable that it is 1-3 mass parts. When the said ratio is less than 0.5 mass part with respect to 100 mass parts of polymers (P), it will become difficult to obtain the storage stability of the water-based metal surface treatment agent of this invention, and when it exceeds 5 mass parts, it will become the tendency for the water resistance of the film obtained to fall. . The emulsifier will be described later.

,β-에틸렌성 불포화 카르복실산 (C) 및/또는 반응성 유화제로부터의 중합 단위를 임의적 구성 단위로서 포함할 수 있는데, 그들 중합 단위를 제외한 나머지의 구성 단위로서 그 모두가 방향 고리를 함유하지 않는 알킬(메트)아크릴레이트 및 하이드록시알킬(메트)아크릴레이트에서 선택되는 적어도 1 종의 (메트)아크릴산에스테르로부터의 중합 단위를 포함한다.As described above, the polymer (P) contains the polymerized unit from the (meth) acrylic acid ester (A) as an essential structural unit, and the polymerized unit from the silicon-containing monomer (B),

polymerizable units from, β-ethylenically unsaturated carboxylic acids (C) and / or reactive emulsifiers may be included as optional structural units, all of which are free of aromatic rings except those polymerizing units. And a polymerization unit from at least one kind of (meth) acrylic acid ester selected from alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate.

It is preferable that carbon number of an alkyl group is 1-10 in the above, It is more preferable that it is 1-6, It is further more preferable that it is 1-4. Moreover, it is preferable that carbon number of a hydroxyalkyl group is 1-10, It is more preferable that it is 1-6, It is further more preferable that it is 1-4.

Specifically as said (meth) acrylic acid ester, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, n -Hexyl acrylate, cyclohexyl acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, methyl methacrylate , Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclo Hexyl methacrylate, octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, decyl meth And the like methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate.

The manufacturing method of a polymer (P) is not specifically limited, A polymer (P) can be manufactured using a conventionally well-known method. For example, the polymer (P) is a method of mixing and polymerizing a polymerization initiator, water, an emulsifier, and a monomer in a batch; Monomer dropping method; It can synthesize | combine using methods, such as the preemulsion method. Moreover, multistage superposition | polymerization, such as seed polymerization, core-shell polymerization, and power feed polymerization, can also be performed and abnormal structure of particle | grains can also be implemented. The polymerization temperature is usually 0 to 100 ° C, preferably 40 to 95 ° C, and the polymerization time is preferably 1 to 10 hours.

A polymerization initiator is not specifically limited, For example, ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, benzoyl peroxide, t-butyl peroxy benzoate, lauroyl peroxide, t-butyl hydroperoxide, etc. can be used. Can be.

In the water-based metal surface treatment agent of the present invention, the polymer (P) is dispersed in water by an emulsifier.

-[1-{(알릴옥시)메틸}-2-(노닐페녹시)에틸]-ω-하이드록시폴리옥시에틸렌,

-술포-ω-(1-(알콕시)메틸-2-(2-프로페닐옥시)에톡시)-폴리(옥시-1,2-에탄디일)염 등을 들 수 있다. 비반응성 유화제로는, 특별히 제한되지 않고, 고급 지방산염 (라우르산나트륨, 올레산나트륨 등), 고급 알코올황산에스테르염 (라우릴황산나트륨, 올레일황산나트륨 등), 고급 알킬아릴술폰산염 (도데실벤젠술폰산나트륨, 도데실디페닐에테르디술폰산나트륨 등), 폴리옥시에틸렌노닐페닐에테르, 폴리옥시에틸렌라우릴에테르, 폴리옥시에틸렌스테아릴에테르, 폴리옥시에틸렌올레일에테르, 폴리에틸렌글리콜모노라우레이트, 폴리에틸렌글리콜모노스테아레이트, 폴리에틸렌글리콜디스테아레이트 등을 들 수 있다. 상기에서 염으로는 나트륨염, 칼륨염, 암모늄염 등을 들 수 있다. An emulsifier can use at least 1 sort (s) chosen from a reactive emulsifier and a non-reactive emulsifier. There is no restriction | limiting in particular as a reactive emulsifier, Vinyl sulfonate, styrene sulfonate, sulfoethyl methacrylate salt, alkyl allyl sulfosuccinate, alkenyl sulfosuccinate, polyoxyalkylene alkenyl ether sulfate, polyoxyalkylene alkenyl Ether, polyoxyethylene alkyl propenyl phenyl ether, polyoxyethylene alkyl propenyl phenyl ether sulfate ester salt, polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ester salt,

-[1-{(allyloxy) methyl} -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene,

-Sulfo-ω- (1- (alkoxy) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) salt and the like. There is no restriction | limiting in particular as a non-reactive emulsifier, A higher fatty acid salt (sodium laurate, sodium oleate, etc.), a higher alcohol sulfate ester salt (sodium lauryl sulfate, sodium oleyl sulfate, etc.), a higher alkyl aryl sulfonate (dodecylbenzene Sodium sulfonate, sodium dodecyldiphenyl ether disulfonate), polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyethylene glycol monolaurate, polyethylene glycol mono Stearates, polyethylene glycol distearate, and the like. Examples of the salts include sodium salts, potassium salts, and ammonium salts.

As the emulsifier, only reactive emulsifiers may be used, or only non-reactive emulsifiers may be used, or they may be used in combination. It is preferable to use a reactive emulsifier in view of reducing the amount of emulsifier used.

The usage-amount when using only a reactive emulsifier as an emulsifier was already mentioned. As a usage-amount when using only a non-reactive emulsifier, it is preferable that it is 3-10 mass parts with respect to 100 mass parts of polymers (P), and it is more preferable that it is 5-8 weight part. If it is less than 3 mass parts, it will become difficult to obtain the storage stability of the water-based metal surface treatment agent of this invention, and when it exceeds 10 mass parts, it will become the tendency for the water resistance of the film obtained to fall. The usage-amount when using a reactive emulsifier and a non-reactive emulsifier together can be determined in consideration of the usage-amount when using only one. As mentioned above, it is preferable that it is 0.5-10 mass parts with respect to 100 mass parts of polymers (P), and, as for the usage-amount as an emulsifier whole, it is more preferable that it is 1-8 mass parts.

The polymer dispersion liquid (emulsion or suspension) or polymer solution obtained by the said superposition | polymerization can be used as a metal surface treating agent as it is or adjusting solid content concentration.

The metal surface treating agent of this invention can contain a plasticizer (Q).

The plasticizer (Q) preferably has at least one ester bond and / or at least one ether bond in the molecule, and 2,2,4-trimethyl-1,3pentanediol monoisobutylate, diethylene glycol monobutyl ether It is more preferable that it is at least 1 sort (s) chosen from acetate, ethylene glycol monobutyl ether, and dipropylene glycol n-butyl ether, and 2,2, 4- trimethyl- 1,3 pentanediol monoisobutylate and / or diethylene glycol mono It is still more preferable that it is butyl ether acetate. If the plasticizer (Q) does not also have an ester bond and an ether bond, it is not preferable because it does not function as a plasticizer of the polymer (P).

It is preferable that it is 0.5-50 mass parts with respect to 100 mass parts of polymers (P), as for the compounding quantity of a plasticizer (Q), it is more preferable that it is 2-45 mass parts, It is further more preferable that it is 5-40 mass parts. When the said compounding quantity is less than 0.5 mass part, the addition effect of a plasticizer (Q) becomes difficult to express, As a result, it becomes difficult to obtain favorable film-forming property, and it becomes difficult to obtain favorable transparency of a film. Moreover, when it exceeds 50 mass parts, there exists a tendency for storage stability to fall.

In addition, the film formation means film formation, and micro means the state in which the particle | grains of the polymer (P) after drying are fused. In the film formation step, the plasticizer (Q) acts as a plasticizer of the polymer (P) to promote fusion of the particles. As a result, diffuse reflection of incident light is suppressed, transparency of the film is increased, alkali resistance and acid resistance are improved, and cohesion force of the film is improved, and thus workability is improved.

The water-based metal surface treatment agent of the present invention may further contain a resin having no C═C double bond as a resin other than the polymer (P) for the purpose of improving chemical resistance and / or corrosion resistance. As such other resin, the acrylic resin which does not have a C = C double bond, an epoxy resin, a urethane resin, etc. are all mentioned. There is no restriction | limiting in particular as another resin, What is common in the aqueous metal surface treating agent can be used, As an acrylic resin, For example, polymethyl (meth) acrylate, poly (meth) acrylate, polyacrylic acid 2- Ethyl hexyl or the like, for example, as an epoxy resin, hydrogenated bisphenol A type epoxy resin, and as a urethane resin, for example, aliphatic diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate and poly Polycondensates with ether polyols (polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.) or polyester polyols (such as condensates of adipic acid and ethylene glycol) can be used.

It is preferable that it is 70 mass parts or less in the case of an acrylic resin, and, as for the compounding quantity of another resin, 100 mass parts of polymers (P), it is more preferable that it is 60 mass parts or less, It is further more preferable that it is 50 mass parts or less; In the case of an epoxy resin, it is preferable that it is 90 mass parts or less, It is more preferable that it is 80 mass parts or less, It is further more preferable that it is 70 mass parts or less; In the case of urethane resin, it is preferable that it is 90 mass parts or less, It is more preferable that it is 80 mass parts or less, It is further more preferable that it is 70 mass parts or less. When it exceeds the preferable range, respectively, it becomes difficult to acquire ultraviolet-ray deterioration resistance, alkali resistance, acid resistance, workability, and film permeability derived from a polymer (P).

The medium of the aqueous metal surface treating agent of the present invention is water.

The aqueous metal surface treatment agent of this invention is a leveling agent for improving applicability in the range which does not impair the effect of this invention; Water-soluble solvent for improving the dryness of a film; Antirust pigment; Colored pigments; Fillers such as liquid or vapor phase silica for improving film density and film hardness; It may contain additives such as wax for improving lubricity. As a leveling agent, a nonionic or cationic surfactant can be used, A polyethylene oxide of polyacetylene glycol, a polypropylene oxide adduct, an acetylene glycol compound, etc. are mentioned, As a water-soluble solvent, ethanol, isopropyl alcohol, t- Alcohols such as butyl alcohol and propylene glycol; Esters such as ethyl acetate and butyl acetate; Ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, etc. are mentioned.

The addition amount of these additives is made into less than 20 mass% with respect to solid content of the surface treating agent as a whole.

It is preferable that it is 10-100 mass%, and, as for the ratio of the polymer (P) to solid content in the aqueous metal surface treatment agent of this invention, ie, the ratio of the polymer (P) in a dry film, it is more preferable that it is 20-100 mass parts, 30 It is further more preferable that it is-100 mass%. When the ratio of polymer (P) is less than 5 mass%, it becomes difficult to obtain ultraviolet-ray resistance, alkali resistance, acid resistance, processability, and film transparency derived from the polymer (P).

In addition, in this invention, since a plasticizer is considered to evaporate in the drying process after application | coating, it is thought that there may be some which remain, but shall not contain in solid content.

It is preferable that it is -5-40 degreeC, and, as for the minimum film forming temperature at the time of applying the aqueous metal surface treating agent of this invention to a metal material, it is more preferable that it is 0-20 degreeC. If the minimum film forming temperature is less than -5 ° C, storage stability tends to be difficult to obtain. When the minimum film forming temperature exceeds 40 ° C, the film forming becomes insufficient, making it difficult to obtain transparency of the film, and also making it difficult to obtain alkali resistance and acid resistance.

It is preferable that it is 3-12, and, as for pH of the aqueous metal surface treating agent of this invention, it is more preferable that it is 5-10. If the pH is less than 3 or more than 12, it becomes difficult to obtain dispersion stability of the polymer (P).

Although solid content concentration in the aqueous metal surface treating agent of this invention is not specifically limited, It is preferable that it is 3-50 mass%, and it is more preferable that it is 5-35 mass%. If it is less than 3 mass%, there exists a possibility that a problem may arise in applicability | paintability, and processing agent cost becomes high. When it exceeds 50 mass%, there exists a tendency for storage stability to fall.

The metal material to which the water-based metal surface treatment agent of the present invention is applied is not particularly limited, and examples thereof include iron, an alloy mainly composed of iron, aluminum, an alloy mainly composed of aluminum, copper, an alloy mainly composed of copper, and the like. It is possible to use a plated metal material, for example, a galvanized steel sheet, which is plated on an arbitrary metal material. The most preferable thing in adapting the water-based metal surface treatment agent of this invention is a galvanized steel plate. As galvanized steel sheet, galvanized steel sheet, zinc-nickel plated steel sheet, zinc-iron plated steel sheet, zinc-chromium plated steel sheet, zinc-aluminum plated steel sheet, zinc-titanium plated steel sheet, zinc-magnesium plated steel sheet, zinc-manganese A plated steel sheet, a zinc-aluminum-magnesium plated steel sheet, a zinc-aluminum-magnesium-silicon plated steel sheet, and the like, and furthermore, these plating layers include cobalt, molybdenum, tungsten, nickel as a small amount of dissimilar metal elements or impurities. And titanium, chromium, aluminum, manganese, iron, magnesium, lead, bismuth, antimony, tin, copper, cadmium, arsenic, and the like, and those in which inorganic substances such as silica, alumina and titania are dispersed. Further, the present invention can also be applied to the above plating and other types of platings, for example, iron plating, iron-phosphorus plating, nickel plating, and cobalt plating. The plating method is not particularly limited, and any method such as a known electroplating method, a hot dip plating method, a vapor deposition plating method, a dispersion plating method, or a vacuum plating method may be used.

The water-based metal surface treatment agent of the present invention is applied to a metal material, preferably at 50 to 250 ° C, more preferably at 70 to 150 ° C, and even more preferably at an arrival temperature (reach metal material temperature) of 100 to 140 ° C. It applies to a metallic material by drying. If the achieved temperature is less than 50 ° C, the solvent of the water-based metal surface treatment agent is not completely volatilized, and if it is higher than 250 ° C, a part of the film formed from the water-based metal surface treatment agent tends to decompose. It is preferable that it is 0.05-5.0 g / m <2>, as for the film mass after drying, it is more preferable that it is 0.2-3.0 g / m <2>, and it is still more preferable that it is 0.5-2.5 g / m <2>. If the film mass is less than 0.05 g / m 2, the surface of the metal material cannot be coated, so that each performance cannot be expressed. If the film mass is greater than 5.0 g / m 2, gas tends to occur during processing, leading to a decrease in operability. .

Example

Although an Example and a comparative example of this invention are given to the following, this invention is concretely demonstrated to it, but this invention is not limited by these.

Preparation of Polymer Dispersion

(1) Component of Polymer

The used (meth) acrylic acid ester (A) is shown below. Styrene (St) was used as a control of (meth) acrylic acid ester (A).

A1: isobornyl acrylate

A2: isobornyl methacrylate

St: styrene (control)

The silicon-containing monomer (B) used is shown below.

B1: vinyl tri (methoxyethoxy) silane

B2: 3-acryloxypropyltrimethoxysilane

B3: 3-methacryloxypropylmethyldimethoxysilane

,β-에틸렌성 불포화 카르복실산 (C) 를 이하에 나타낸다.Used

, (beta) -ethylenically unsaturated carboxylic acid (C) is shown below.

C1: acrylic acid

C2: methacrylic acid

The used emulsifier is as follows.

S1: Eleminol JS-2 as a reactive emulsifier (manufactured by Sanyo Chemical Co., Ltd .; alkylallyl sulfosuccinate)

S2: LN2025D as a non-reactive emulsifier (Teika Co., Ltd. product; sodium dodecylbenzenesulfonate)

Other monomers used are methyl methacrylate (MMA), 2-ethylhexyl acrylate (2 EHA) and butyl acrylate (BA).

(2) Production Example of Polymer Dispersion

In a four-necked flask equipped with a stirrer, a reflux cooler, a dropping funnel and a thermometer, 150 parts by mass of ion-exchanged water and 3 parts by mass of eleminol JS-2 were added after replacing the internal air with nitrogen gas. Into the dropping funnel, 10 parts by mass of isobornyl methacrylate, 44.5 parts by mass of MMA, 37.0 parts by mass of BA, 1 part by mass of vinyltri (methoxyethoxy) silane and 4.5 parts by mass of acrylic acid were mixed and mixed to obtain a mixed monomer. Subsequently, after raising the flask to 70 ° C, 10% by mass of the mixed monomer was added to the flask, followed by 0.3% by mass of ammonium persulfate. After the reaction was completed, 90 mass% of the remaining mixed monomers was added dropwise in 3 hours. After completion of the dropwise addition, the flask temperature was maintained at 75 ° C. for 1 hour to obtain a polymer dispersion.

Preparation of Surface Treatment Liquid

(1) Components other than the polymer (P)

The used plasticizer is as follows.

Q1: 2,2,4-trimethyl-1,3-pentanediol monoisobutylate

Q2: diethylene glycol monobutyl ether acetate

Q3: Ethylene Glycol Monobutyl Ether

Q4: dipropylene glycol mono n-butyl ether

Q5: N-methyl-2-pyrrolidone (control)

The other resin used was as follows.

R1: Hexaethylene glycol type | mold polyether polyurethane resin

R2: Bisphenol A Polyether Polyurethane Resin

(2) Production Example of Surface Treatment Liquid

The polymer dispersion liquid obtained above was cooled to 40 degreeC, adjusted to pH7 in ammonia water, and 30 mass parts of diethylene glycol monobutyl ether acetates were added as a plasticizer, and the surface treatment liquid of Example 25 was manufactured.

(3) Preparation of Surface Treatment Liquid

The surface treatment liquid as an example is shown in Table 1, and the surface treatment liquid as a comparative example is shown in Table 2 which manufactured according to the manufacture example of a surface treatment liquid. In addition, the solid content concentration of the surface treatment liquid was adjusted to 30 mass%.

Trial

(1) material

Commercially available materials shown below were used.

Hot-dip galvanized steel sheet (GI): plate thickness = 0.8 mm, apparent weight = 60/60 (g / ㎡)

Hot-dip zinc-55% aluminum alloy plated steel sheet (GL): plate thickness = 0.8 mm, apparent weight = 150/150 (g / ㎡)

(2) degreasing treatment

Fine cleaner 4336 (trademark: manufactured by Nihon Parkarizing Co., Ltd.), a silicate-based alkali degreasing agent, was dissolved in water at a concentration of 20 g / l, and the resulting solution was sprayed for 2 minutes under conditions of a temperature of 60 ° C and purified water After washing with water for 30 seconds, it was dried.

(3) The coating material after drying by bar coating was applied to the raw material after the degreasing treatment of one of the surface treatment liquid as an example shown in Table 1 and the surface treatment liquid as a comparative example shown in Table 2, and the highest It dried at 80 degreeC of arrival board temperature, and set it as the test board.

Assessment Methods

(1) storage stability

When each surface treatment liquid prepared above was left to stand in 40 degreeC atmosphere, storage stability was evaluated in the period until it gelatinizes.

(Evaluation standard)

◎: 6 months or more

○: 3 months or more, less than 6 months

△: 1 month or more, less than 3 months

×: less than 1 month

The performance of each test plate was evaluated by the following evaluation method.

(2) UV resistance

In a fluorescent ultraviolet light wetting device (UVCON fluorescent light wet light exposure tester), the ultraviolet light of 365 nm was irradiated for 4 hours, and after that, the conditions of standing for 2 hours at an ambient temperature of 50 ° C. and a humidity of 60% Rh as 30 cycles were used as 30 cycles. Cycling was performed and ultraviolet-ray degradation was evaluated by the color tone change ((DELTA) E) before and behind a test.

Color measurement was performed using a Color Meter ZE 2000 (manufactured by NIPPON DENSHOKU, light source: halogen lamp 12 V / 2 A). The color tone measurement in the evaluation of following alkali resistance and acid resistance is also the same.

(Evaluation standard)

◎: ΔE <1

ΔE<3 ○: 1

ΔE <3

ΔE<7 △: 3

ΔE <7

ΔE ×: 7

ΔE

(3) alkali resistance

It was immersed in 3 mass% sodium hydroxide aqueous solution at 25 degreeC for 1 hour, and alkali resistance was evaluated by the color tone change ((DELTA) E) before and behind a test.

(Evaluation standard)

◎: ΔE <1

ΔE<3 ○: 1

ΔE <3

ΔE<7 △: 3

ΔE <7

ΔE ×: 7

ΔE

(4) acid resistance

It was immersed in 3 mass% hydrochloric acid at 25 degreeC for 1 hour, and acid resistance was evaluated by the color tone change ((DELTA) E) before and behind a test.

(Evaluation standard)

◎: ΔE <1

ΔE<3 ○: 1

ΔE <3

ΔE<7 △: 3

ΔE <7

ΔE×: 7

ΔE

(5) processability

Workability was evaluated in the flaw state of the evaluation surface after the draw bead test by the universal testing machine. The drawing conditions were 0.5 ton of crimp load, bead tip radius 5 mm, bead height 5 mm, and drawing speed 5 cm / sec.

(Evaluation standard)

◎: no scratch

○: There are some scratches

(Triangle | delta): Partial sticking generate | occur | produced.

X: The sticking occurred all over.

(6) film transparency

Film transparency was evaluated by the brightness change ((DELTA) L) before and behind surface treatment. Brightness measurement was performed using the Color Meter ZE2000 (manufactured by NIPPON DENSHOKU, light source: halogen lamp 12 V / 2 A).

(Evaluation standard)

◎: -1 <ΔL <1

-1, 또는 1

ΔL<5 ○: -5 <ΔL

-1, or 1

ΔL <5

-5, 또는 5

ΔL<10 △: -10 <ΔL

-5, or 5

ΔL <10

-10, 또는 10

ΔL×: ΔL

-10, or 10

ΔL

,β-에틸렌성 불포화 카르복실산 (C) 를 사용하는 경우에는, 내자외선 열화성, 내산성 및 피막 투명성이 오르는 경향이 있고 ; 유화제로서 반응성 유화제를 사용하는 경우에는, 비반응성 유화제를 사용하는 경우에 비하여, 동등한 효과를 증대시키는 데 유화제의 사용량을 줄일 수 있고 ; 바람직한 가소제를 사용하는 경우에는 그렇지 않은 가소제를 사용하는 경우에 비하여, 피막 투명성이 우수한 것을 알 수 있다.The evaluation results are shown in Tables 3 to 6. In Table 3-Table 6, ultraviolet-resistant is meaning of ultraviolet-ray deterioration. From the comparison of the corresponding examples and the comparative examples, when the essential requirements are within the scope of the present invention, when the Tg is too low, the storage stability, ultraviolet ray deterioration resistance, alkali resistance, acid resistance, processability and film transparency are excellent. Alkali resistance, acid resistance and workability are poor, and when Tg is too high, storage stability, alkali resistance, acid resistance, processability and film transparency are inferior; Moreover, when styrene is used instead of (meth) acrylic acid ester (A) or what has C = C double bond as another resin, ultraviolet-ray deterioration resistance is inferior; Moreover, when other (meth) acrylic acid ester is used instead of (meth) acrylic acid ester (A), it turns out that alkali resistance, acid resistance, and workability are inferior. Moreover, when using a silicon-containing monomer (B) from a comparison between Examples, storage stability becomes low, but ultraviolet-ray deterioration resistance increases;

In the case of using the? -ethylenically unsaturated carboxylic acid (C), ultraviolet ray deterioration resistance, acid resistance and film transparency tend to increase; When using a reactive emulsifier as an emulsifier, compared with the case of using a non-reactive emulsifier, the usage-amount of an emulsifier can be reduced in order to increase the equivalent effect; When using a preferable plasticizer, it turns out that it is excellent in film transparency compared with the case of using the plasticizer which is not.

Claims (13)

It has a polymer unit from isobornyl (meth) acrylate (A) in a molecule | numerator, contains a polymer (P), a plasticizer (Q), an emulsifier, and water whose glass transition temperature is 0-70 degreeC, and a polymer (P) Is dispersed by the emulsifier, and the plasticizer (Q) is 2,2,4-trimethyl-1,3 pentanediol monoisobutylate, diethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether and dipropylene glycol n It is at least 1 sort (s) chosen from butyl ether, and metal content of a plasticizer (Q) is 0.5-50 mass parts with respect to 100 mass parts of polymers (P). The method of claim 1,
Polymer (P) is of general formula (III)
(3)

[In formula, R <6>, R <7> and R <8> represent a hydrogen atom, a hydroxyl group, a C1-C3 alkyl group, a C1-C3 alkoxy group, or a C1-C3 alkoxyl alkoxy group independently of each other, X is the formula (IV)
[Chemical Formula 4]

Or general formula (V)
[Chemical Formula 5]

(In formula, R9 represents a hydrogen atom or a methyl group, R10 represents a group represented by a C1-C12 alkylene group.) The processing agent which has a polymerization unit from the silicon-containing monomer (B) represented by a molecule | numerator. The method of claim 1,
Polymer (P)

A treating agent having, in a molecule, a polymerized unit from? -ethylenically unsaturated carboxylic acid (C). The method of claim 2,
Polymer (P)

A treating agent having, in a molecule, a polymerized unit from? -ethylenically unsaturated carboxylic acid (C). The method of claim 1,
An emulsifier is a reactive agent present in the polymer (P) as a polymer unit from the reactive emulsifier. The method of claim 1,
Alkyl (meth) acrylates and hydroxyalkyl (meth) acryl, in which all of the remaining structural units of the polymer (P), except the polymerized unit from isobornyl (meth) acrylate (A), do not contain an aromatic ring At least 1 sort (s) of (meth) acrylic acid ester chosen from the rate, The processing agent which is a polymerization unit from the C1-C10 thing of an alkyl group or a hydroxyalkyl group. The method of claim 5, wherein
Alkyl (meth) acrylate in which all of the remaining structural units of the polymer (P) except for the polymerized unit from isobornyl (meth) acrylate (A) and the polymerized unit from the reactive emulsifier do not contain an aromatic ring, and At least 1 sort (s) of (meth) acrylic acid ester chosen from hydroxyalkyl (meth) acrylate, The processing agent which is a polymerization unit from the C1-C10 thing of an alkyl group or a hydroxyalkyl group. The method according to any one of claims 1 to 7,
The processing agent whose ratio of the polymerization unit from isobornyl (meth) acrylate (A) is 0.1-50 mass parts with respect to 100 mass parts of polymers (P). The method according to claim 2 or 4,
The processing agent whose ratio of the polymerization unit from a silicon-containing monomer (B) is 0.5-2.0 mass parts with respect to 100 mass parts of polymers (P). The method of claim 3, wherein
The processing agent whose acid value of a polymer (P) is 15-30 mgKOH / g. delete delete delete