WO2017159732A1 - Coating resin composition - Google Patents
Coating resin composition Download PDFInfo
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- WO2017159732A1 WO2017159732A1 PCT/JP2017/010395 JP2017010395W WO2017159732A1 WO 2017159732 A1 WO2017159732 A1 WO 2017159732A1 JP 2017010395 W JP2017010395 W JP 2017010395W WO 2017159732 A1 WO2017159732 A1 WO 2017159732A1
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- coating
- resin composition
- resin
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
Definitions
- the present invention relates to a coating resin composition.
- a method for drying in a short time for example, a method using a one-pack type acrylic resin-based paint can be mentioned.
- one-component paints can be dried in a relatively short time, but their coating properties such as adhesion and chemical resistance are not always sufficient.
- a two-component paint is known in which an acrylic resin and an isocyanate resin are reacted. In this case, although the coating film properties are good, the acrylic resin and the isocyanate resin are not dried. Since there is a problem of storage stability such that gelation occurs because the reaction progresses before the paint is prepared and applied, since the drying time is relatively long. Actual use was limited.
- Patent Documents 1 and 2 As a method for solving this problem, for example, a method for improving the storage stability by covering the surface of the curing agent with fine particles (for example, Patent Documents 1 and 2) has been reported. However, the range of use is limited. As another method, a method of modifying a novolak resin with a compound having an aminotriazine ring structure as a curing agent has been reported (for example, Patent Document 3). However, the curing agent has a complicated structure and a compatible solvent or epoxy. Since the resin types are limited, the range of use is limited.
- the present invention provides a coating resin composition that has storage stability and quick drying properties that can withstand use in a production line, and that is excellent in coating film properties such as adhesion and chemical resistance of the coating film. Objective.
- the present inventor has, as essential components, a polyfunctional reactive compound having a specific number of epoxy groups and / or halohydrin groups and an amino resin having a specific number average molecular weight.
- the two-part epoxy resin composition contains excellent storage stability and quick-drying, and is excellent in coating film properties such as adhesion and chemical resistance, which are the characteristics of the two-part paint.
- the present invention has been completed by finding that it can be suitably used as a coating composition for application to a coating.
- the coating resin composition of the present invention is a composition for applying to a resin substrate, (A) a polyfunctional reactive compound having 2 to 15 epoxy groups and / or halohydrin groups in one molecule; and (B) An amino resin having a number average molecular weight of 250 to 10,000 is included.
- the (B) amino resin is preferably a melamine resin.
- the content of the component (B) is preferably 10 to 10,000 parts by weight with respect to 100 parts by weight of the component (A).
- the polyfunctional reactive compound has 2 to 10 epoxy groups and / or halohydrin groups in one molecule.
- the member of this invention has a resin base material and the coating film formed on the resin base material using the resin composition for coating of this invention, It is characterized by the above-mentioned.
- the resin base material is preferably polyester.
- the member manufacturing method of the present invention is a method for manufacturing the member of the present invention, A step (1) of applying the coating resin composition of the present invention to at least one surface of a resin substrate; and Step (2) in which the coating resin composition applied in step (1) is cured by heating at 60 to 250 ° C. for 5 to 300 seconds. It is characterized by including.
- the coating resin composition of the present invention contains a polyfunctional reactive compound having a specific number of epoxy groups and / or halohydrin groups and an amino resin having a specific number average molecular weight, the storage stability and quick drying properties are improved. While being excellent, it is excellent in the adhesiveness and chemical resistance of a coating film, and is suitably used as a coating composition for coating on a resin substrate.
- the coating resin composition of the present invention is a composition for applying to a resin substrate, (A) a polyfunctional reactive compound having 2 to 15 epoxy groups and / or halohydrin groups in one molecule; and (B) An amino resin having a number average molecular weight of 250 to 10,000 is included.
- the polyfunctional reactive compound (hereinafter also simply referred to as the component (A)) is not particularly limited as long as it has 2 to 15 epoxy groups and / or halohydrin groups in one molecule.
- the polyfunctional reactive compound (hereinafter also simply referred to as the component (A)) is not particularly limited as long as it has 2 to 15 epoxy groups and / or halohydrin groups in one molecule.
- halohydrin compound examples include compounds obtained by reacting halogen and water with a compound having a double bond, and compounds obtained by reacting epihalohydrins and alcohol compounds in the presence of a Lewis acid catalyst (halohydrin). Ether compounds). Examples include sorbitol polyhalohydrin, glycerin polyhalohydrin, diglycerin polychlorohydrin, ethylene glycol dihalohydrin, propylene glycol dichlorohydrin. These may be used alone or in combination of two or more.
- the number of epoxy groups and / or halohydrin groups that component (A) has in one molecule is not particularly limited as long as it is 2 to 15, but is preferably 2 to 10, and preferably 2 to 6 Is more preferable, and 2 to 4 is more preferable. If the number of epoxy groups and / or halohydrin groups in the molecule (A) is less than 2, the crosslinking reaction required to cure the resin composition and form a coating film is impossible. If it exceeds 15, the storage stability may be lowered.
- the epoxy equivalent is not particularly limited, but is preferably 100 to 1000, more preferably 120 to 700. When the epoxy equivalent is less than 100, curing may be poor, and when it exceeds 1000, the storage stability may be deteriorated.
- hydrolyzable chlorine is not particularly limited, but is usually 10% to 30%.
- the content of the component (A) is not particularly limited, but is preferably 1 to 90% by weight, and more preferably 1 to 50% by weight. If the content is less than 1% by weight, the component (A) may be insufficient and the crosslinking reaction may not sufficiently proceed, resulting in curing failure. If the content exceeds 90% by weight, the component (B) is insufficient. In some cases, the crosslinking reaction does not proceed sufficiently, resulting in poor curing.
- component (B) Amino resin (hereinafter also simply referred to as component (B)) is blended as a curing agent for component (A) in the coating resin composition of the present invention.
- component (B) Amino resin (hereinafter also simply referred to as component (B)) is blended as a curing agent for component (A) in the coating resin composition of the present invention.
- the reason why the storage stability is improved by using the component (B) is that the number average molecular weight of the component (B) is relatively large, and the amino group involved in the reaction with the component (A) is the component (B) at room temperature. It is considered that the reaction with the component (A) hardly occurs because it is inside the three-dimensional structure.
- the reason why the quick drying property when cured by heating is improved by using the component (B) is that the amino group is highly reactive with the component (A) in the first place, and the three-dimensional structure of the component (B) by heating This is probably because the reaction with the component (A) proceeds immediately when the amino group changes and the amino group appears on the surface.
- the component (B) is not particularly limited as long as the number average molecular weight is 250 to 10,000, and examples thereof include melamine resin containing benzoguanamine resin, urea resin, and glyoxal resin. These may be used alone or in combination of two or more. In these, a melamine resin is preferable from a viewpoint of the intensity
- the melamine resin is a polycondensate of melamine or a derivative thereof and an aldehyde compound.
- a monomer constituting the melamine resin for example, methylolmelamine, benzoguanamine or the like can be used as the melamine or derivative thereof, and formaldehyde or the like can be used as the aldehyde compound. Can be used. These monomers of melamine or a derivative thereof and an aldehyde compound may be used alone or in combination of two or more.
- the number average molecular weight of the component (B) is not particularly limited as long as it is 250 to 10,000, but is preferably 500 to 2,000, and more preferably 700 to 1,300. When the number average molecular weight is less than 250, quick drying may be insufficient, and when it exceeds 10,000, compatibility with the component (A) may be insufficient.
- the content of the component (B) is not particularly limited, but is preferably 10 to 10,000 parts by weight with respect to 100 parts by weight of the component (A). More preferred are parts by weight. When the content of the component (B) is less than 10 parts by weight or more than 10,000 parts by weight, the quick drying property may be insufficient.
- the coating resin composition of the present invention may optionally contain other components as long as the object of the present invention is not impaired.
- other components include, but are not limited to, solvents, curing accelerators, antifoaming agents, leveling agents, organic thickeners, antioxidants, light stabilizers, adhesion improvers, mold release agents, and reinforcing materials. , Softeners, colorants, flame retardants, antistatic agents, wetting and dispersing agents, and the like.
- the solvent is not particularly limited, and any of water-based and organic solvent-based solvents can be suitably used.
- aromatic hydrocarbon solvents such as toluene, ethylbenzene, trimethylbenzene, and xylene
- fats such as pentane, hexane, and cyclohexane.
- Aromatic hydrocarbon solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, methyl cellosolve, ethyl cellosolve, Glycol ether solvents such as butyl cellosolve, methyl diglycol, ethyl diglycol, butyl diglycol, propylene glycol monomethyl ether, ethyl acetate, butyl acetate Ester solvents such as propylene glycol monomethyl ether acetate, water and the like.
- Examples of commercially available products that can be used as the aromatic hydrocarbon solvent include Solvesso 100, Solvesso 150, Solvesso 200, and the like. These may be used alone or in combination of two or more.
- the content may be selected depending on the coating method and the desired thickness of the cured coating film, and is not particularly limited.
- the amount is preferably 10 to 5000 parts by weight, more preferably 20 to 2000 parts by weight.
- the content is less than 10 parts by weight, the viscosity becomes high and uniform coating may not be possible.
- the content exceeds 5000 parts by weight, a coating film having a sufficient film thickness may not be obtained. And not preferable from the viewpoint of VOC reduction.
- the curing accelerator is not particularly limited.
- formic acid, acetic acid, lactic acid, glycolic acid, butyric acid, isobutyric acid, propionic acid, caproic acid, octanoic acid, heptanoic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid and thioglycol Aliphatic carboxylic acids such as acids, polycarboxylic acids such as malic acid, oxalic acid, succinic acid, malonic acid, fumaric acid, maleic acid, tartaric acid and citric acid, benzoic acid, p-toluic acid, p-aminobenzoic acid, p-chlorobenzoic acid, benzoic acid derivatives such as 2,4-dichlorobenzoic acid, phthalic acid derivatives such as phthalic acid, isophthalic acid and terephthalic acid, and aromatic carboxylic acids such as salicylic acid, phenol
- the coating resin composition of the present invention contains a curing accelerator
- its content is not particularly limited, but is preferably 0.01 to 2000 parts by weight with respect to 100 parts by weight of component (A), More preferred is 0.1 to 2000 parts by weight.
- the content is less than 0.01 parts by weight, the effect of adding a curing accelerator may not be sufficiently obtained.
- the content exceeds 2000 parts by weight, the appearance of the coating film may be impaired. It may not be preferable also from a viewpoint.
- the member of this invention has a resin base material and the coating film formed on the resin base material using the resin composition for coating of this invention, It is characterized by the above-mentioned.
- the material of the resin base material is not particularly limited. Polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene, polypropylene, and polymethylpentene, polyamides such as nylon 6 and nylon 66, polycarbonate, polyvinyl acetate, polyimide , ABS resin and the like. Among these, polyester is preferable from the viewpoints of economy and processability.
- the thickness of the resin base material is not particularly limited, and a resin base material that is formed into various molded products such as a film, a sheet, a plate, a laminate, and the like manufactured by a molding process can be used.
- the coating film is formed on the resin substrate using the coating resin composition of the present invention.
- a method for forming a coating film on a resin substrate using the coating resin composition of the present invention is not particularly limited, but the coating resin composition of the present invention was applied to at least one surface of the resin substrate. Thereafter, a method of heating and curing can be used. The method for applying the coating resin composition of the present invention and the method for curing by heating will be described later.
- the thickness of the coating film is not particularly limited, but is preferably 0.1 to 30 ⁇ m, and more preferably 0.3 to 20 ⁇ m. When the thickness is less than 0.1 ⁇ m, the smoothness of the coating film may be insufficient, and when it exceeds 30 ⁇ m, the adhesion may be insufficient due to an increase in internal stress.
- the member manufacturing method of the present invention is a method for manufacturing the member of the present invention, A step (1) of applying the coating resin composition of the present invention to at least one surface of a resin substrate; and Step (2) in which the coating resin composition applied in step (1) is cured by heating at 60 to 250 ° C. for 5 to 300 seconds. It is characterized by including.
- the coating resin composition of the present invention is applied to at least one surface of the resin substrate.
- the method for applying the coating resin composition of the present invention is not particularly limited.
- Die coating method, air doctor coating method, blade coating method, rod coating method, curtain coating method, knife coating method, transfer roll coating method, squeeze coating method, impregnation coating method, kiss coating method, calendar coating method, extrusion coating method, etc. Can be mentioned.
- Step (2)> the coating resin composition applied in step (1) is heated and cured.
- the heating temperature is not particularly limited, but is preferably 60 to 250 ° C, more preferably 60 to 150 ° C.
- the heating temperature is less than 60 ° C.
- curing may be poor, and when it exceeds 250 ° C., the shape of the substrate may be impaired depending on the material of the resin substrate.
- the heating time is not particularly limited as long as it is 5 to 300 seconds, but is preferably 20 to 120 seconds.
- the heating time is less than 5 seconds, curing may be poor, and when it exceeds 300 seconds, the shape of the substrate may be damaged depending on the material of the resin substrate, and the time required for the process is long. Therefore, it is not preferable from the viewpoint of productivity.
- Examples 1 to 3, Comparative Examples 1 to 4 Each component was mixed by the weight ratio shown in following Table 1, and the resin composition for coating was obtained. The storage stability was evaluated by the method described later using the obtained resin composition for coating. Further, the obtained coating resin composition is applied onto a resin substrate using a bar coater (No. 2), and cured by heating at 130 ° C. for 60 seconds using a hot air dryer to form a coating film. To obtain a member. Using the sample cooled to room temperature as a test piece, quick drying, adhesion and chemical resistance were evaluated by the methods described below. These results are shown in Table 1.
- the gauze impregnated with methyl ethyl ketone was reciprocated 30 times in a state where it was pressed against the coating surface of the test piece under the condition of a load of 300 g. And was evaluated in two stages according to the following criteria. ⁇ : No peeling ⁇ : With peeling
- the coating resin composition of the present invention can be sufficiently dried even under low temperature and short drying conditions of 130 ° C. and 60 seconds, and the coating film has good adhesion and chemical resistance. It was. On the other hand, Comparative Examples 1 to 4 which are conventional techniques cannot be sufficiently dried under low temperature and short time drying conditions, and as a result, adhesion and chemical resistance are insufficient.
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Abstract
Provided is a coating resin composition which has storage stability and rapid-drying properties that make the coating resin composition usable on manufacturing lines and which gives coating films excellent in terms of adhesion, chemical resistance, etc.
The present invention relates to a coating resin composition for application to resinous bases, characterized by comprising
(A) a polyfunctional reactive compound having two to fifteen epoxy and/or halohydrin groups in the molecule and
(B) an amino resin having a number-average molecular weight of 250-10,000.
Description
本発明は、コーティング用樹脂組成物に関する。
The present invention relates to a coating resin composition.
従来、樹脂基材を用いた工業製品は、例えばパソコンの筺体や各種フィルム等の形状の違いはあるが広く普及している。これらの製造方法に共通することとして、製造ラインで塗装から乾燥までを一貫して行うという点が挙げられる。上記の様に製造ラインで塗装から乾燥までを一貫して行う際には、その工程に要する時間が生産性へと直結する。そのため、生産性を向上させるために上記工程を短時間で完了させる必要がある。
2. Description of the Related Art Conventionally, industrial products using a resin base material have been widely used, although there are differences in the shapes of personal computer housings and various films, for example. Common to these production methods is that the production line is consistently performed from painting to drying. As described above, when the production line is consistently performed from painting to drying, the time required for the process is directly linked to productivity. Therefore, in order to improve productivity, it is necessary to complete the said process in a short time.
短時間での乾燥を行う方法としては、例えば一液型のアクリル樹脂系塗料を用いる方法が挙げられる。しかし、基本的な技術情報として既に認知されている様に、一液型塗料は比較的短時間での乾燥が可能であるものの、密着性や耐薬品性等の塗膜物性が必ずしも十分ではない。この点を改善する方法としては、例えばアクリル樹脂とイソシアネート樹脂とを反応させる二液型塗料が知られているが、この場合、塗膜物性は良好であるものの、乾燥時にアクリル樹脂とイソシアネート樹脂とを反応させる必要があるために比較的乾燥時間が長く、また、塗料を調製して塗装するまでの間にも反応が進行するためにゲル化等が起こるといった貯蔵安定性の問題があるため、実際の使用は限られたものであった。
As a method for drying in a short time, for example, a method using a one-pack type acrylic resin-based paint can be mentioned. However, as already recognized as basic technical information, one-component paints can be dried in a relatively short time, but their coating properties such as adhesion and chemical resistance are not always sufficient. . As a method for improving this point, for example, a two-component paint is known in which an acrylic resin and an isocyanate resin are reacted. In this case, although the coating film properties are good, the acrylic resin and the isocyanate resin are not dried. Since there is a problem of storage stability such that gelation occurs because the reaction progresses before the paint is prepared and applied, since the drying time is relatively long. Actual use was limited.
二液型塗料を短時間で乾燥させる方法としては、乾燥温度を高温にする方法や比較的反応性の高い樹脂同士を組み合わせる方法がある。しかし、樹脂基材はその耐熱性の問題から、樹脂基材の材質や乾燥時間による違いはあるものの、一般的には高温での処理は困難である。そのため、現実的には塗料に用いる樹脂種の選択による解決が行われる。樹脂種としては、例えばエポキシ樹脂とアミン化合物等の硬化剤との組み合わせが広く知られているが、速乾性と貯蔵安定性とはトレードオフの関係にあり、これらの両立は一般的に困難である。この課題を解決する方法として、例えば硬化剤の表面を微粒子で覆うことで貯蔵安定性を向上させる方法（例えば、特許文献１、２）が報告されているが、この方法では微粒子が塗膜中に残留する問題が有り、その使用範囲は制限されるものである。その他の方法としては、硬化剤としてアミノトリアジン環構造を持つ化合物でノボラック樹脂を変性する方法（例えば、特許文献３）が報告されているが、硬化剤の構造が複雑で相溶する溶剤やエポキシ樹脂種が限られるため、その使用範囲は制限されるものである。
As a method of drying the two-component paint in a short time, there are a method of increasing the drying temperature and a method of combining resins having relatively high reactivity. However, due to the heat resistance problem of resin base materials, processing at high temperatures is generally difficult, although there are differences depending on the material of the resin base material and the drying time. Therefore, in reality, a solution is made by selecting a resin type used for the paint. As a resin type, for example, a combination of an epoxy resin and a curing agent such as an amine compound is widely known, but quick drying and storage stability are in a trade-off relationship, and it is generally difficult to achieve both of them. is there. As a method for solving this problem, for example, a method for improving the storage stability by covering the surface of the curing agent with fine particles (for example, Patent Documents 1 and 2) has been reported. However, the range of use is limited. As another method, a method of modifying a novolak resin with a compound having an aminotriazine ring structure as a curing agent has been reported (for example, Patent Document 3). However, the curing agent has a complicated structure and a compatible solvent or epoxy. Since the resin types are limited, the range of use is limited.
本発明は、製造ラインでの使用に耐えうる貯蔵安定性及び速乾性を有し、かつ、塗膜の密着性及び耐薬品性等の塗膜物性に優れるコーティング用樹脂組成物を提供することを目的とする。
The present invention provides a coating resin composition that has storage stability and quick drying properties that can withstand use in a production line, and that is excellent in coating film properties such as adhesion and chemical resistance of the coating film. Objective.
本発明者は、上記課題を解決するために鋭意検討した結果、特定数のエポキシ基及び／又はハロヒドリン基を有する多官能反応性化合物と、特定の数平均分子量を有するアミノ樹脂とを必須成分として含む二液型のエポキシ樹脂組成物が、貯蔵安定性及び速乾性に優れ、かつ、二液型塗料の特徴である塗膜の密着性及び耐薬品性等の塗膜物性に優れ、樹脂基材に塗布するためのコーティング用組成物として好適に用いられることを見出し、本発明を完成させた。
As a result of intensive studies to solve the above problems, the present inventor has, as essential components, a polyfunctional reactive compound having a specific number of epoxy groups and / or halohydrin groups and an amino resin having a specific number average molecular weight. The two-part epoxy resin composition contains excellent storage stability and quick-drying, and is excellent in coating film properties such as adhesion and chemical resistance, which are the characteristics of the two-part paint. The present invention has been completed by finding that it can be suitably used as a coating composition for application to a coating.
すなわち、本発明のコーティング用樹脂組成物は、樹脂基材に塗布するための組成物であって、
（Ａ）１分子中にエポキシ基及び／又はハロヒドリン基を２～１５個有する多官能反応性化合物、及び、
（Ｂ）数平均分子量２５０～１０，０００のアミノ樹脂
を含むことを特徴とする。 That is, the coating resin composition of the present invention is a composition for applying to a resin substrate,
(A) a polyfunctional reactive compound having 2 to 15 epoxy groups and / or halohydrin groups in one molecule; and
(B) An amino resin having a number average molecular weight of 250 to 10,000 is included.
（Ａ）１分子中にエポキシ基及び／又はハロヒドリン基を２～１５個有する多官能反応性化合物、及び、
（Ｂ）数平均分子量２５０～１０，０００のアミノ樹脂
を含むことを特徴とする。 That is, the coating resin composition of the present invention is a composition for applying to a resin substrate,
(A) a polyfunctional reactive compound having 2 to 15 epoxy groups and / or halohydrin groups in one molecule; and
(B) An amino resin having a number average molecular weight of 250 to 10,000 is included.
本発明のコーティング用樹脂組成物において、（Ｂ）アミノ樹脂がメラミン樹脂であることが好ましい。
In the coating resin composition of the present invention, the (B) amino resin is preferably a melamine resin.
本発明のコーティング用樹脂組成物において、（Ｂ）成分の含有量が（Ａ）成分１００重量部に対して１０～１０，０００重量部であることが好ましい。
In the coating resin composition of the present invention, the content of the component (B) is preferably 10 to 10,000 parts by weight with respect to 100 parts by weight of the component (A).
本発明のコーティング用樹脂組成物において、（Ａ）多官能反応性化合物が１分子中にエポキシ基及び／又はハロヒドリン基を２～１０個有することが好ましい。
In the coating resin composition of the present invention, it is preferable that (A) the polyfunctional reactive compound has 2 to 10 epoxy groups and / or halohydrin groups in one molecule.
本発明の部材は、樹脂基材と、本発明のコーティング用樹脂組成物を用いて樹脂基材上に形成された塗膜とを有することを特徴とする。
The member of this invention has a resin base material and the coating film formed on the resin base material using the resin composition for coating of this invention, It is characterized by the above-mentioned.
本発明の部材において、樹脂基材の材質がポリエステルであることが好ましい。
In the member of the present invention, the resin base material is preferably polyester.
本発明の部材の製造方法は、本発明の部材を製造するための方法であって、
本発明のコーティング用樹脂組成物を樹脂基材の少なくとも一つの面に塗布する工程（１）、及び、
工程（１）で塗布したコーティング用樹脂組成物を６０～２５０℃で５～３００秒間加熱して硬化させる工程（２）
を含むことを特徴とする。 The member manufacturing method of the present invention is a method for manufacturing the member of the present invention,
A step (1) of applying the coating resin composition of the present invention to at least one surface of a resin substrate; and
Step (2) in which the coating resin composition applied in step (1) is cured by heating at 60 to 250 ° C. for 5 to 300 seconds.
It is characterized by including.
本発明のコーティング用樹脂組成物を樹脂基材の少なくとも一つの面に塗布する工程（１）、及び、
工程（１）で塗布したコーティング用樹脂組成物を６０～２５０℃で５～３００秒間加熱して硬化させる工程（２）
を含むことを特徴とする。 The member manufacturing method of the present invention is a method for manufacturing the member of the present invention,
A step (1) of applying the coating resin composition of the present invention to at least one surface of a resin substrate; and
Step (2) in which the coating resin composition applied in step (1) is cured by heating at 60 to 250 ° C. for 5 to 300 seconds.
It is characterized by including.
本発明のコーティング用樹脂組成物は、特定数のエポキシ基及び／又はハロヒドリン基を有する多官能反応性化合物と、特定の数平均分子量を有するアミノ樹脂とを含むため、貯蔵安定性及び速乾性に優れるとともに、塗膜の密着性及び耐薬品性に優れ、樹脂基材に塗布するためのコーティング用組成物として好適に用いられる。
Since the coating resin composition of the present invention contains a polyfunctional reactive compound having a specific number of epoxy groups and / or halohydrin groups and an amino resin having a specific number average molecular weight, the storage stability and quick drying properties are improved. While being excellent, it is excellent in the adhesiveness and chemical resistance of a coating film, and is suitably used as a coating composition for coating on a resin substrate.
＜＜コーティング用樹脂組成物＞＞
本発明のコーティング用樹脂組成物は、樹脂基材に塗布するための組成物であって、
（Ａ）１分子中にエポキシ基及び／又はハロヒドリン基を２～１５個有する多官能反応性化合物、及び、
（Ｂ）数平均分子量２５０～１０，０００のアミノ樹脂
を含むことを特徴とする。 << Resin composition for coating >>
The coating resin composition of the present invention is a composition for applying to a resin substrate,
(A) a polyfunctional reactive compound having 2 to 15 epoxy groups and / or halohydrin groups in one molecule; and
(B) An amino resin having a number average molecular weight of 250 to 10,000 is included.
本発明のコーティング用樹脂組成物は、樹脂基材に塗布するための組成物であって、
（Ａ）１分子中にエポキシ基及び／又はハロヒドリン基を２～１５個有する多官能反応性化合物、及び、
（Ｂ）数平均分子量２５０～１０，０００のアミノ樹脂
を含むことを特徴とする。 << Resin composition for coating >>
The coating resin composition of the present invention is a composition for applying to a resin substrate,
(A) a polyfunctional reactive compound having 2 to 15 epoxy groups and / or halohydrin groups in one molecule; and
(B) An amino resin having a number average molecular weight of 250 to 10,000 is included.
＜（Ａ）多官能反応性化合物＞
（Ａ）多官能反応性化合物（以下、単に（Ａ）成分ともいう）としては、１分子中にエポキシ基及び／又はハロヒドリン基を２～１５個有する限り特に限定されず、エポキシ基を有する化合物として例えば、ソルビトールポリグリシジルエーテル、ビスフェノールＡジグリシジルエーテル、グリセリンポリグリシジルエーテル、ポリグリセリンポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、レゾルシノールジグリシジルエーテル、イソソルビドジグリシジルエーテル、イソマンニドジグリシジルエーテル、イソイディットジグリシジルエーテル、水添ビスフェノールＡジグリシジルエーテル、クレゾールノボラックポリグリシジルエーテル等が挙げられる。ハロヒドリン化合物としては、例えば、ハロゲンと水を、二重結合をもつ化合物に反応させて得られる化合物や、エピハロヒドリン類とアルコール化合物とをルイス酸触媒存在下で反応させて得られる化合物（ハロヒドリンエーテル化合物）を挙げることができる。例えば、ソルビトールポリハロヒドリン、グリセリンポリハロヒドリン、ジグリセリンポリクロロヒドリン、エチレングリコールジハロヒドリン、プロピレングリコールジクロロヒドリンなどが挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。 <(A) polyfunctional reactive compound>
(A) The polyfunctional reactive compound (hereinafter also simply referred to as the component (A)) is not particularly limited as long as it has 2 to 15 epoxy groups and / or halohydrin groups in one molecule. For example, sorbitol polyglycidyl ether, bisphenol A diglycidyl ether, glycerin polyglycidyl ether, polyglycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, resorcinol diglycidyl ether, isosorbide diglycidyl ether, isomanni Examples include dodiglycidyl ether, isoidid diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and cresol novolac polyglycidyl ether. Examples of the halohydrin compound include compounds obtained by reacting halogen and water with a compound having a double bond, and compounds obtained by reacting epihalohydrins and alcohol compounds in the presence of a Lewis acid catalyst (halohydrin). Ether compounds). Examples include sorbitol polyhalohydrin, glycerin polyhalohydrin, diglycerin polychlorohydrin, ethylene glycol dihalohydrin, propylene glycol dichlorohydrin. These may be used alone or in combination of two or more.
（Ａ）多官能反応性化合物（以下、単に（Ａ）成分ともいう）としては、１分子中にエポキシ基及び／又はハロヒドリン基を２～１５個有する限り特に限定されず、エポキシ基を有する化合物として例えば、ソルビトールポリグリシジルエーテル、ビスフェノールＡジグリシジルエーテル、グリセリンポリグリシジルエーテル、ポリグリセリンポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、レゾルシノールジグリシジルエーテル、イソソルビドジグリシジルエーテル、イソマンニドジグリシジルエーテル、イソイディットジグリシジルエーテル、水添ビスフェノールＡジグリシジルエーテル、クレゾールノボラックポリグリシジルエーテル等が挙げられる。ハロヒドリン化合物としては、例えば、ハロゲンと水を、二重結合をもつ化合物に反応させて得られる化合物や、エピハロヒドリン類とアルコール化合物とをルイス酸触媒存在下で反応させて得られる化合物（ハロヒドリンエーテル化合物）を挙げることができる。例えば、ソルビトールポリハロヒドリン、グリセリンポリハロヒドリン、ジグリセリンポリクロロヒドリン、エチレングリコールジハロヒドリン、プロピレングリコールジクロロヒドリンなどが挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。 <(A) polyfunctional reactive compound>
(A) The polyfunctional reactive compound (hereinafter also simply referred to as the component (A)) is not particularly limited as long as it has 2 to 15 epoxy groups and / or halohydrin groups in one molecule. For example, sorbitol polyglycidyl ether, bisphenol A diglycidyl ether, glycerin polyglycidyl ether, polyglycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, resorcinol diglycidyl ether, isosorbide diglycidyl ether, isomanni Examples include dodiglycidyl ether, isoidid diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and cresol novolac polyglycidyl ether. Examples of the halohydrin compound include compounds obtained by reacting halogen and water with a compound having a double bond, and compounds obtained by reacting epihalohydrins and alcohol compounds in the presence of a Lewis acid catalyst (halohydrin). Ether compounds). Examples include sorbitol polyhalohydrin, glycerin polyhalohydrin, diglycerin polychlorohydrin, ethylene glycol dihalohydrin, propylene glycol dichlorohydrin. These may be used alone or in combination of two or more.
（Ａ）成分が１分子中に有するエポキシ基及び／又はハロヒドリン基の数は、２～１５個である限り特に限定されないが、２～１０個であることが好ましく、２～６個であることがより好ましく、２～４個であることがさらに好ましい。（Ａ）成分が１分子中に有するエポキシ基及び／又はハロヒドリン基の数が２個未満であると、樹脂組成物を硬化させて塗膜を形成するために必要な架橋反応が不可能であり、１５個を超えると、貯蔵安定性が低下することがある。
The number of epoxy groups and / or halohydrin groups that component (A) has in one molecule is not particularly limited as long as it is 2 to 15, but is preferably 2 to 10, and preferably 2 to 6 Is more preferable, and 2 to 4 is more preferable. If the number of epoxy groups and / or halohydrin groups in the molecule (A) is less than 2, the crosslinking reaction required to cure the resin composition and form a coating film is impossible. If it exceeds 15, the storage stability may be lowered.
（Ａ）成分がエポキシ化合物の場合、エポキシ当量は、特に限定されないが、１００～１０００であることが好ましく、１２０～７００であることがより好ましい。エポキシ当量が１００未満であると、硬化不良となることがあり、１０００を超えると、貯蔵安定性が悪くなることがある。（Ａ）成分がハロヒドリン基を有する化合物の場合、加水分解性塩素は特に限定されないが、通常１０％～３０％である。
When the component (A) is an epoxy compound, the epoxy equivalent is not particularly limited, but is preferably 100 to 1000, more preferably 120 to 700. When the epoxy equivalent is less than 100, curing may be poor, and when it exceeds 1000, the storage stability may be deteriorated. In the case where the component (A) is a compound having a halohydrin group, hydrolyzable chlorine is not particularly limited, but is usually 10% to 30%.
本発明のコーティング用樹脂組成物において、（Ａ）成分の含有量は、特に限定されないが、１～９０重量％であることが好ましく、１～５０重量％であることがより好ましい。含有量が１重量％未満であると、（Ａ）成分が不足することで十分に架橋反応が進まずに硬化不良となることがあり、９０重量％を超えると、（Ｂ）成分が不足することで十分に架橋反応が進まずに硬化不良となることがある。
In the coating resin composition of the present invention, the content of the component (A) is not particularly limited, but is preferably 1 to 90% by weight, and more preferably 1 to 50% by weight. If the content is less than 1% by weight, the component (A) may be insufficient and the crosslinking reaction may not sufficiently proceed, resulting in curing failure. If the content exceeds 90% by weight, the component (B) is insufficient. In some cases, the crosslinking reaction does not proceed sufficiently, resulting in poor curing.
＜（Ｂ）アミノ樹脂＞
（Ｂ）アミノ樹脂（以下、単に（Ｂ）成分ともいう）は、本発明のコーティング用樹脂組成物において（Ａ）成分の硬化剤として配合される。（Ｂ）成分を用いることで貯蔵安定性が向上する理由としては、（Ｂ）成分の数平均分子量が比較的大きく、（Ａ）成分との反応に関与するアミノ基が常温では（Ｂ）成分の立体構造の内側にあるため、（Ａ）成分との反応が起こりにくいことが考えられる。また、（Ｂ）成分を用いることで加熱により硬化させる際の速乾性が向上する理由としては、アミノ基はそもそも（Ａ）成分との反応性が高く、加熱により（Ｂ）成分の立体構造が変化しアミノ基が表面に現れると即座に（Ａ）成分との反応が進行するためと考えられる。 <(B) Amino resin>
(B) Amino resin (hereinafter also simply referred to as component (B)) is blended as a curing agent for component (A) in the coating resin composition of the present invention. The reason why the storage stability is improved by using the component (B) is that the number average molecular weight of the component (B) is relatively large, and the amino group involved in the reaction with the component (A) is the component (B) at room temperature. It is considered that the reaction with the component (A) hardly occurs because it is inside the three-dimensional structure. In addition, the reason why the quick drying property when cured by heating is improved by using the component (B) is that the amino group is highly reactive with the component (A) in the first place, and the three-dimensional structure of the component (B) by heating This is probably because the reaction with the component (A) proceeds immediately when the amino group changes and the amino group appears on the surface.
（Ｂ）アミノ樹脂（以下、単に（Ｂ）成分ともいう）は、本発明のコーティング用樹脂組成物において（Ａ）成分の硬化剤として配合される。（Ｂ）成分を用いることで貯蔵安定性が向上する理由としては、（Ｂ）成分の数平均分子量が比較的大きく、（Ａ）成分との反応に関与するアミノ基が常温では（Ｂ）成分の立体構造の内側にあるため、（Ａ）成分との反応が起こりにくいことが考えられる。また、（Ｂ）成分を用いることで加熱により硬化させる際の速乾性が向上する理由としては、アミノ基はそもそも（Ａ）成分との反応性が高く、加熱により（Ｂ）成分の立体構造が変化しアミノ基が表面に現れると即座に（Ａ）成分との反応が進行するためと考えられる。 <(B) Amino resin>
(B) Amino resin (hereinafter also simply referred to as component (B)) is blended as a curing agent for component (A) in the coating resin composition of the present invention. The reason why the storage stability is improved by using the component (B) is that the number average molecular weight of the component (B) is relatively large, and the amino group involved in the reaction with the component (A) is the component (B) at room temperature. It is considered that the reaction with the component (A) hardly occurs because it is inside the three-dimensional structure. In addition, the reason why the quick drying property when cured by heating is improved by using the component (B) is that the amino group is highly reactive with the component (A) in the first place, and the three-dimensional structure of the component (B) by heating This is probably because the reaction with the component (A) proceeds immediately when the amino group changes and the amino group appears on the surface.
（Ｂ）成分としては、数平均分子量が２５０～１０，０００である限り特に限定されず、例えば、ベンゾグアナミン樹脂を含むメラミン樹脂、尿素樹脂、グリオキザール樹脂等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。これらの中では、塗膜の強度や密着性の観点からメラミン樹脂が好ましい。メラミン樹脂とは、メラミン又はその誘導体とアルデヒド化合物の重縮合物であり、メラミン樹脂を構成するモノマーとしては、例えばメラミン又はその誘導体としてメチロールメラミン、ベンゾグアナミン等を用いることができ、アルデヒド化合物としてホルムアルデヒド等を用いることができる。これらメラミン又はその誘導体とアルデヒド化合物の各モノマーは、単独で用いても良いし、２種類以上を併用しても良い。
The component (B) is not particularly limited as long as the number average molecular weight is 250 to 10,000, and examples thereof include melamine resin containing benzoguanamine resin, urea resin, and glyoxal resin. These may be used alone or in combination of two or more. In these, a melamine resin is preferable from a viewpoint of the intensity | strength of a coating film, or adhesiveness. The melamine resin is a polycondensate of melamine or a derivative thereof and an aldehyde compound. As a monomer constituting the melamine resin, for example, methylolmelamine, benzoguanamine or the like can be used as the melamine or derivative thereof, and formaldehyde or the like can be used as the aldehyde compound. Can be used. These monomers of melamine or a derivative thereof and an aldehyde compound may be used alone or in combination of two or more.
（Ｂ）成分の数平均分子量は、２５０～１０，０００である限り特に限定されないが、５００～２，０００であることが好ましく、７００～１，３００であることがより好ましい。数平均分子量が２５０未満であると、速乾性が不十分となることがあり、１０，０００を超えると、（Ａ）成分との相溶性が不十分となることがある。
The number average molecular weight of the component (B) is not particularly limited as long as it is 250 to 10,000, but is preferably 500 to 2,000, and more preferably 700 to 1,300. When the number average molecular weight is less than 250, quick drying may be insufficient, and when it exceeds 10,000, compatibility with the component (A) may be insufficient.
本発明のコーティング用樹脂組成物において、（Ｂ）成分の含有量は、特に限定されないが、（Ａ）成分１００重量部に対して１０～１０，０００重量部であることが好ましく、１０～５００重量部であることがより好ましい。（Ｂ）成分の含有量が１０重量部未満の場合や１０，０００重量部を超える場合には、速乾性が不十分となることがある。
In the coating resin composition of the present invention, the content of the component (B) is not particularly limited, but is preferably 10 to 10,000 parts by weight with respect to 100 parts by weight of the component (A). More preferred are parts by weight. When the content of the component (B) is less than 10 parts by weight or more than 10,000 parts by weight, the quick drying property may be insufficient.
本発明のコーティング用樹脂組成物は、（Ａ）成分及び（Ｂ）成分に加えて、本発明の目的を損なわない範囲内で、任意に他の成分を含有していても良い。他の成分としては、特に限定されないが、例えば、溶剤、硬化促進剤、消泡剤、レベリング剤、有機増粘剤、酸化防止剤、光安定剤、接着性向上剤、離型剤、補強材、軟化剤、着色剤、難燃剤、帯電防止剤、湿潤分散剤等が挙げられる。
In addition to the component (A) and the component (B), the coating resin composition of the present invention may optionally contain other components as long as the object of the present invention is not impaired. Examples of other components include, but are not limited to, solvents, curing accelerators, antifoaming agents, leveling agents, organic thickeners, antioxidants, light stabilizers, adhesion improvers, mold release agents, and reinforcing materials. , Softeners, colorants, flame retardants, antistatic agents, wetting and dispersing agents, and the like.
＜溶剤＞
溶剤としては、特に限定はなく、水系又は有機溶剤系の何れも好適に使用できるが、例えば、トルエン、エチルベンゼン、トリメチルベンゼン、キシレン等の芳香族炭化水素系溶剤、ペンタン、ヘキサン、シクロヘキサン等の脂肪族炭化水素系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤、メタノール、エタノール、イソプロパノール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール等のアルコール系溶剤、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルジグリコール、エチルジグリコール、ブチルジグリコール、プロピレングリコールモノメチルエーテル等のグリコールエーテル系溶剤、酢酸エチル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート等のエステル系溶剤、水等が挙げられる。また、芳香族炭化水素系溶剤として使用できる市販品としては、ソルベッソ１００、ソルベッソ１５０、ソルベッソ２００等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。 <Solvent>
The solvent is not particularly limited, and any of water-based and organic solvent-based solvents can be suitably used. For example, aromatic hydrocarbon solvents such as toluene, ethylbenzene, trimethylbenzene, and xylene, and fats such as pentane, hexane, and cyclohexane. Aromatic hydrocarbon solvents, acetone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, methyl cellosolve, ethyl cellosolve, Glycol ether solvents such as butyl cellosolve, methyl diglycol, ethyl diglycol, butyl diglycol, propylene glycol monomethyl ether, ethyl acetate, butyl acetate Ester solvents such as propylene glycol monomethyl ether acetate, water and the like. Examples of commercially available products that can be used as the aromatic hydrocarbon solvent include Solvesso 100, Solvesso 150, Solvesso 200, and the like. These may be used alone or in combination of two or more.
溶剤としては、特に限定はなく、水系又は有機溶剤系の何れも好適に使用できるが、例えば、トルエン、エチルベンゼン、トリメチルベンゼン、キシレン等の芳香族炭化水素系溶剤、ペンタン、ヘキサン、シクロヘキサン等の脂肪族炭化水素系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤、メタノール、エタノール、イソプロパノール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール等のアルコール系溶剤、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルジグリコール、エチルジグリコール、ブチルジグリコール、プロピレングリコールモノメチルエーテル等のグリコールエーテル系溶剤、酢酸エチル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート等のエステル系溶剤、水等が挙げられる。また、芳香族炭化水素系溶剤として使用できる市販品としては、ソルベッソ１００、ソルベッソ１５０、ソルベッソ２００等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。 <Solvent>
The solvent is not particularly limited, and any of water-based and organic solvent-based solvents can be suitably used. For example, aromatic hydrocarbon solvents such as toluene, ethylbenzene, trimethylbenzene, and xylene, and fats such as pentane, hexane, and cyclohexane. Aromatic hydrocarbon solvents, acetone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, methyl cellosolve, ethyl cellosolve, Glycol ether solvents such as butyl cellosolve, methyl diglycol, ethyl diglycol, butyl diglycol, propylene glycol monomethyl ether, ethyl acetate, butyl acetate Ester solvents such as propylene glycol monomethyl ether acetate, water and the like. Examples of commercially available products that can be used as the aromatic hydrocarbon solvent include Solvesso 100, Solvesso 150, Solvesso 200, and the like. These may be used alone or in combination of two or more.
本発明のコーティング用樹脂組成物が溶剤を含有する場合、その含有量は、塗布方法、所望する硬化塗膜の膜厚によって選択すればよく、特に限定されないが、（Ａ）成分１００重量部に対して１０～５０００重量部であることが好ましく、２０～２０００重量部であることがより好ましい。含有量が１０重量部未満であると、粘度が高くなり、均一に塗工できないことがあり、５０００重量部を超えると、十分な膜厚の塗膜が得られないことがある他、経済性やＶＯＣ削減の観点から好ましくない。
When the coating resin composition of the present invention contains a solvent, the content may be selected depending on the coating method and the desired thickness of the cured coating film, and is not particularly limited. The amount is preferably 10 to 5000 parts by weight, more preferably 20 to 2000 parts by weight. When the content is less than 10 parts by weight, the viscosity becomes high and uniform coating may not be possible. When the content exceeds 5000 parts by weight, a coating film having a sufficient film thickness may not be obtained. And not preferable from the viewpoint of VOC reduction.
＜硬化促進剤＞
硬化促進剤としては、特に限定されないが、例えば、ギ酸、酢酸、乳酸、グリコール酸、酪酸、イソ酪酸、プロピオン酸、カプロン酸、オクタン酸、ヘプタン酸、クロロ酢酸、ジクロロ酢酸、トリクロロ酢酸及びチオグリコール酸等の脂肪族カルボン酸類、リンゴ酸、シュウ酸、コハク酸、マロン酸、フマル酸、マレイン酸、酒石酸及びクエン酸等のポリカルボン酸類、安息香酸、ｐ－トルイル酸、ｐ－アミノ安息香酸、ｐ－クロロ安息香酸、２, ４－ジクロロ安息香酸等の安息香酸誘導体、フタル酸、イソフタル酸及びテレフタル酸等のフタル酸誘導体及びサリチル酸等の芳香族カルボン酸類、フェノール、ｍ－クレゾール、ｐ－クロロフェノール、ｐ－ニトロフェノール、２，４－ジクロロフェノール、ｏ－アミノフェノール、ｐ－アミノフェノール及び２，４，５－トリクロロフェノール等のフェノール類、レゾルシノール、ハイドロキノン、カテコール及びフロログルシノール等のポリフェノール類、ノボラック等のフェノール樹脂類、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブチルアルコール、ｔｅｒｔ－ブチルアルコール等の脂肪族アルコール類、エチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール等のグリコール類、グリセリン、ポリグリセリン等のグリセロール類、トルエンスルホン酸、メタンスルホン酸等のスルホン酸類等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。 <Curing accelerator>
The curing accelerator is not particularly limited. For example, formic acid, acetic acid, lactic acid, glycolic acid, butyric acid, isobutyric acid, propionic acid, caproic acid, octanoic acid, heptanoic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid and thioglycol Aliphatic carboxylic acids such as acids, polycarboxylic acids such as malic acid, oxalic acid, succinic acid, malonic acid, fumaric acid, maleic acid, tartaric acid and citric acid, benzoic acid, p-toluic acid, p-aminobenzoic acid, p-chlorobenzoic acid, benzoic acid derivatives such as 2,4-dichlorobenzoic acid, phthalic acid derivatives such as phthalic acid, isophthalic acid and terephthalic acid, and aromatic carboxylic acids such as salicylic acid, phenol, m-cresol, p-chloro Phenol, p-nitrophenol, 2,4-dichlorophenol, o-aminophenol, p-amino Phenols such as phenol and 2,4,5-trichlorophenol, polyphenols such as resorcinol, hydroquinone, catechol and phloroglucinol, phenol resins such as novolac, methanol, ethanol, propanol, isopropanol, butanol, isobutyl alcohol, tert -Aliphatic alcohols such as butyl alcohol, glycols such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol, glycerols such as glycerin and polyglycerin, and sulfonic acids such as toluenesulfonic acid and methanesulfonic acid . These may be used alone or in combination of two or more.
硬化促進剤としては、特に限定されないが、例えば、ギ酸、酢酸、乳酸、グリコール酸、酪酸、イソ酪酸、プロピオン酸、カプロン酸、オクタン酸、ヘプタン酸、クロロ酢酸、ジクロロ酢酸、トリクロロ酢酸及びチオグリコール酸等の脂肪族カルボン酸類、リンゴ酸、シュウ酸、コハク酸、マロン酸、フマル酸、マレイン酸、酒石酸及びクエン酸等のポリカルボン酸類、安息香酸、ｐ－トルイル酸、ｐ－アミノ安息香酸、ｐ－クロロ安息香酸、２, ４－ジクロロ安息香酸等の安息香酸誘導体、フタル酸、イソフタル酸及びテレフタル酸等のフタル酸誘導体及びサリチル酸等の芳香族カルボン酸類、フェノール、ｍ－クレゾール、ｐ－クロロフェノール、ｐ－ニトロフェノール、２，４－ジクロロフェノール、ｏ－アミノフェノール、ｐ－アミノフェノール及び２，４，５－トリクロロフェノール等のフェノール類、レゾルシノール、ハイドロキノン、カテコール及びフロログルシノール等のポリフェノール類、ノボラック等のフェノール樹脂類、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブチルアルコール、ｔｅｒｔ－ブチルアルコール等の脂肪族アルコール類、エチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール等のグリコール類、グリセリン、ポリグリセリン等のグリセロール類、トルエンスルホン酸、メタンスルホン酸等のスルホン酸類等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。 <Curing accelerator>
The curing accelerator is not particularly limited. For example, formic acid, acetic acid, lactic acid, glycolic acid, butyric acid, isobutyric acid, propionic acid, caproic acid, octanoic acid, heptanoic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid and thioglycol Aliphatic carboxylic acids such as acids, polycarboxylic acids such as malic acid, oxalic acid, succinic acid, malonic acid, fumaric acid, maleic acid, tartaric acid and citric acid, benzoic acid, p-toluic acid, p-aminobenzoic acid, p-chlorobenzoic acid, benzoic acid derivatives such as 2,4-dichlorobenzoic acid, phthalic acid derivatives such as phthalic acid, isophthalic acid and terephthalic acid, and aromatic carboxylic acids such as salicylic acid, phenol, m-cresol, p-chloro Phenol, p-nitrophenol, 2,4-dichlorophenol, o-aminophenol, p-amino Phenols such as phenol and 2,4,5-trichlorophenol, polyphenols such as resorcinol, hydroquinone, catechol and phloroglucinol, phenol resins such as novolac, methanol, ethanol, propanol, isopropanol, butanol, isobutyl alcohol, tert -Aliphatic alcohols such as butyl alcohol, glycols such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol, glycerols such as glycerin and polyglycerin, and sulfonic acids such as toluenesulfonic acid and methanesulfonic acid . These may be used alone or in combination of two or more.
本発明のコーティング用樹脂組成物が硬化促進剤を含有する場合、その含有量は、特に限定されないが、（Ａ）成分１００重量部に対して０．０１～２０００重量部であることが好ましく、０．１～２０００重量部であることがより好ましい。含有量が０．０１重量部未満であると、硬化促進剤を添加する効果が十分に得られないことがあり、２０００重量部を超えると、塗膜外観が損なわれることがあり、経済性の観点からも好ましくないことがある。
When the coating resin composition of the present invention contains a curing accelerator, its content is not particularly limited, but is preferably 0.01 to 2000 parts by weight with respect to 100 parts by weight of component (A), More preferred is 0.1 to 2000 parts by weight. When the content is less than 0.01 parts by weight, the effect of adding a curing accelerator may not be sufficiently obtained. When the content exceeds 2000 parts by weight, the appearance of the coating film may be impaired. It may not be preferable also from a viewpoint.
＜＜部材＞＞
本発明の部材は、樹脂基材と、本発明のコーティング用樹脂組成物を用いて樹脂基材上に形成された塗膜とを有することを特徴とする。 << Member >>
The member of this invention has a resin base material and the coating film formed on the resin base material using the resin composition for coating of this invention, It is characterized by the above-mentioned.
本発明の部材は、樹脂基材と、本発明のコーティング用樹脂組成物を用いて樹脂基材上に形成された塗膜とを有することを特徴とする。 << Member >>
The member of this invention has a resin base material and the coating film formed on the resin base material using the resin composition for coating of this invention, It is characterized by the above-mentioned.
＜樹脂基材＞
樹脂基材の材質は、特に限定されないが、ポリエチレンテレフタラート、ポリエチレンナフタレート等のポリエステル、ポリエチレン、ポリプロピレン、ポリメチルペンテン等のポリオレフィン、ナイロン６、ナイロン６６等のポリアミド、ポリカーボネート、ポリ酢酸ビニル、ポリイミド、ＡＢＳ樹脂等が挙げられる。これらの中では、経済性、加工容易性の観点からポリエステルが好ましい。 <Resin substrate>
The material of the resin base material is not particularly limited. Polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene, polypropylene, and polymethylpentene, polyamides such as nylon 6 and nylon 66, polycarbonate, polyvinyl acetate, polyimide , ABS resin and the like. Among these, polyester is preferable from the viewpoints of economy and processability.
樹脂基材の材質は、特に限定されないが、ポリエチレンテレフタラート、ポリエチレンナフタレート等のポリエステル、ポリエチレン、ポリプロピレン、ポリメチルペンテン等のポリオレフィン、ナイロン６、ナイロン６６等のポリアミド、ポリカーボネート、ポリ酢酸ビニル、ポリイミド、ＡＢＳ樹脂等が挙げられる。これらの中では、経済性、加工容易性の観点からポリエステルが好ましい。 <Resin substrate>
The material of the resin base material is not particularly limited. Polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene, polypropylene, and polymethylpentene, polyamides such as nylon 6 and nylon 66, polycarbonate, polyvinyl acetate, polyimide , ABS resin and the like. Among these, polyester is preferable from the viewpoints of economy and processability.
樹脂基材の厚みは、特に限定されず、フィルム、シート、板、積層体等、成形加工等により製造される様々な成形品に成形されたものを樹脂基材として用いることができる。
The thickness of the resin base material is not particularly limited, and a resin base material that is formed into various molded products such as a film, a sheet, a plate, a laminate, and the like manufactured by a molding process can be used.
＜塗膜＞
塗膜は、本発明のコーティング用樹脂組成物を用いて樹脂基材上に形成される。本発明のコーティング用樹脂組成物を用いて樹脂基材上に塗膜を形成する方法としては、特に限定されないが、本発明のコーティング用樹脂組成物を樹脂基材の少なくとも一つの面に塗布した後、加熱して硬化させる方法等が挙げられる。本発明のコーティング用樹脂組成物を塗布する方法、及び、加熱して硬化させる方法については、後述する。 <Coating film>
The coating film is formed on the resin substrate using the coating resin composition of the present invention. A method for forming a coating film on a resin substrate using the coating resin composition of the present invention is not particularly limited, but the coating resin composition of the present invention was applied to at least one surface of the resin substrate. Thereafter, a method of heating and curing can be used. The method for applying the coating resin composition of the present invention and the method for curing by heating will be described later.
塗膜は、本発明のコーティング用樹脂組成物を用いて樹脂基材上に形成される。本発明のコーティング用樹脂組成物を用いて樹脂基材上に塗膜を形成する方法としては、特に限定されないが、本発明のコーティング用樹脂組成物を樹脂基材の少なくとも一つの面に塗布した後、加熱して硬化させる方法等が挙げられる。本発明のコーティング用樹脂組成物を塗布する方法、及び、加熱して硬化させる方法については、後述する。 <Coating film>
The coating film is formed on the resin substrate using the coating resin composition of the present invention. A method for forming a coating film on a resin substrate using the coating resin composition of the present invention is not particularly limited, but the coating resin composition of the present invention was applied to at least one surface of the resin substrate. Thereafter, a method of heating and curing can be used. The method for applying the coating resin composition of the present invention and the method for curing by heating will be described later.
塗膜の厚みは、特に限定されないが、０．１～３０μｍであることが好ましく、０．３～２０μｍであることがより好ましい。厚みが０．１μｍ未満であると、塗膜の平滑性が不十分となることがあり、３０μｍを超えると、内部応力の増加により密着性が不十分となることがある。
The thickness of the coating film is not particularly limited, but is preferably 0.1 to 30 μm, and more preferably 0.3 to 20 μm. When the thickness is less than 0.1 μm, the smoothness of the coating film may be insufficient, and when it exceeds 30 μm, the adhesion may be insufficient due to an increase in internal stress.
＜＜部材の製造方法＞＞
本発明の部材の製造方法は、本発明の部材を製造するための方法であって、
本発明のコーティング用樹脂組成物を樹脂基材の少なくとも一つの面に塗布する工程（１）、及び、
工程（１）で塗布したコーティング用樹脂組成物を６０～２５０℃で５～３００秒間加熱して硬化させる工程（２）
を含むことを特徴とする。 << Member manufacturing method >>
The member manufacturing method of the present invention is a method for manufacturing the member of the present invention,
A step (1) of applying the coating resin composition of the present invention to at least one surface of a resin substrate; and
Step (2) in which the coating resin composition applied in step (1) is cured by heating at 60 to 250 ° C. for 5 to 300 seconds.
It is characterized by including.
本発明の部材の製造方法は、本発明の部材を製造するための方法であって、
本発明のコーティング用樹脂組成物を樹脂基材の少なくとも一つの面に塗布する工程（１）、及び、
工程（１）で塗布したコーティング用樹脂組成物を６０～２５０℃で５～３００秒間加熱して硬化させる工程（２）
を含むことを特徴とする。 << Member manufacturing method >>
The member manufacturing method of the present invention is a method for manufacturing the member of the present invention,
A step (1) of applying the coating resin composition of the present invention to at least one surface of a resin substrate; and
Step (2) in which the coating resin composition applied in step (1) is cured by heating at 60 to 250 ° C. for 5 to 300 seconds.
It is characterized by including.
＜工程（１）＞
本工程では、本発明のコーティング用樹脂組成物を樹脂基材の少なくとも一つの面に塗布する。本発明のコーティング用樹脂組成物を塗布する方法としては、特に限定されないが、例えば、バーコート法、スピンコート法、スプレーコート法、ディップコート法、ノズルコート法、グラビアコート法、リバースロールコート法、ダイコート法、エアドクターコート法、ブレードコート法、ロッドコート法、カーテンコート法、ナイフコート法、トランスファロールコート法、スクイズコート法、含浸コート法、キスコート法、カレンダコート法、押出コート法等が挙げられる。 <Step (1)>
In this step, the coating resin composition of the present invention is applied to at least one surface of the resin substrate. The method for applying the coating resin composition of the present invention is not particularly limited. For example, a bar coating method, a spin coating method, a spray coating method, a dip coating method, a nozzle coating method, a gravure coating method, a reverse roll coating method. , Die coating method, air doctor coating method, blade coating method, rod coating method, curtain coating method, knife coating method, transfer roll coating method, squeeze coating method, impregnation coating method, kiss coating method, calendar coating method, extrusion coating method, etc. Can be mentioned.
本工程では、本発明のコーティング用樹脂組成物を樹脂基材の少なくとも一つの面に塗布する。本発明のコーティング用樹脂組成物を塗布する方法としては、特に限定されないが、例えば、バーコート法、スピンコート法、スプレーコート法、ディップコート法、ノズルコート法、グラビアコート法、リバースロールコート法、ダイコート法、エアドクターコート法、ブレードコート法、ロッドコート法、カーテンコート法、ナイフコート法、トランスファロールコート法、スクイズコート法、含浸コート法、キスコート法、カレンダコート法、押出コート法等が挙げられる。 <Step (1)>
In this step, the coating resin composition of the present invention is applied to at least one surface of the resin substrate. The method for applying the coating resin composition of the present invention is not particularly limited. For example, a bar coating method, a spin coating method, a spray coating method, a dip coating method, a nozzle coating method, a gravure coating method, a reverse roll coating method. , Die coating method, air doctor coating method, blade coating method, rod coating method, curtain coating method, knife coating method, transfer roll coating method, squeeze coating method, impregnation coating method, kiss coating method, calendar coating method, extrusion coating method, etc. Can be mentioned.
＜工程（２）＞
本工程では、工程（１）で塗布したコーティング用樹脂組成物を加熱して硬化させる。 <Step (2)>
In this step, the coating resin composition applied in step (1) is heated and cured.
本工程では、工程（１）で塗布したコーティング用樹脂組成物を加熱して硬化させる。 <Step (2)>
In this step, the coating resin composition applied in step (1) is heated and cured.
工程（２）において、加熱温度は特に限定されないが、６０～２５０℃であることが好ましく、６０～１５０℃であることがより好ましい。加熱温度が６０℃未満であると、硬化不良となることがあり、２５０℃を超えると、樹脂基材の材質によっては基材の形状が損なわれることがある。また、加熱時間は、５～３００秒間である限り特に限定されないが、２０～１２０秒間であることが好ましい。加熱時間が５秒間未満であると、硬化不良となることがあり、３００秒間を超えると、樹脂基材の材質によっては基材の形状が損なわれることがあり、また、工程に要する時間が長くなるため生産性の観点からも好ましくない。
In the step (2), the heating temperature is not particularly limited, but is preferably 60 to 250 ° C, more preferably 60 to 150 ° C. When the heating temperature is less than 60 ° C., curing may be poor, and when it exceeds 250 ° C., the shape of the substrate may be impaired depending on the material of the resin substrate. The heating time is not particularly limited as long as it is 5 to 300 seconds, but is preferably 20 to 120 seconds. When the heating time is less than 5 seconds, curing may be poor, and when it exceeds 300 seconds, the shape of the substrate may be damaged depending on the material of the resin substrate, and the time required for the process is long. Therefore, it is not preferable from the viewpoint of productivity.
以下、実施例を挙げて本発明を説明するが、本発明は以下の実施例に限定されない。以下、「部」又は「％」は特記ない限り、それぞれ「重量部」又は「重量％」を意味する。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to a following example. Hereinafter, “part” or “%” means “part by weight” or “% by weight”, respectively, unless otherwise specified.
（合成例１）
ソルビトール５０ｇをトルエン２０ｇに分散させ、四塩化すず０．１８ｇを添加し、撹拌しながら、９５℃以上１００℃以下の温度範囲にて、エピクロルヒドリン６２ｇを２時間かけて添加し、反応させた。エピクロルヒドリンの消失をＪＩＳ Ｋ ７２３６に記載された滴定法により確認し、溶剤として使用したトルエンを減圧濃縮で除去した。得られた濃縮物を水１００ｇに溶解させ、ソルビトールポリクロルヒドリン化合物の水溶液（全固形分濃度５２．５％）を得た。 (Synthesis Example 1)
50 g of sorbitol was dispersed in 20 g of toluene, 0.18 g of tin tetrachloride was added, and 62 g of epichlorohydrin was added over 2 hours in the temperature range of 95 ° C. or more and 100 ° C. or less while stirring. The disappearance of epichlorohydrin was confirmed by a titration method described in JIS K 7236, and toluene used as a solvent was removed by concentration under reduced pressure. The obtained concentrate was dissolved in 100 g of water to obtain an aqueous solution of sorbitol polychlorohydrin compound (total solid content concentration 52.5%).
ソルビトール５０ｇをトルエン２０ｇに分散させ、四塩化すず０．１８ｇを添加し、撹拌しながら、９５℃以上１００℃以下の温度範囲にて、エピクロルヒドリン６２ｇを２時間かけて添加し、反応させた。エピクロルヒドリンの消失をＪＩＳ Ｋ ７２３６に記載された滴定法により確認し、溶剤として使用したトルエンを減圧濃縮で除去した。得られた濃縮物を水１００ｇに溶解させ、ソルビトールポリクロルヒドリン化合物の水溶液（全固形分濃度５２．５％）を得た。 (Synthesis Example 1)
50 g of sorbitol was dispersed in 20 g of toluene, 0.18 g of tin tetrachloride was added, and 62 g of epichlorohydrin was added over 2 hours in the temperature range of 95 ° C. or more and 100 ° C. or less while stirring. The disappearance of epichlorohydrin was confirmed by a titration method described in JIS K 7236, and toluene used as a solvent was removed by concentration under reduced pressure. The obtained concentrate was dissolved in 100 g of water to obtain an aqueous solution of sorbitol polychlorohydrin compound (total solid content concentration 52.5%).
（使用材料）
下記の実施例及び比較例においては、以下の材料を使用した。
・（Ａ）多官能反応性化合物
ソルビトールポリグリシジルエーテル（ナガセケムテックス株式会社製、デナコールＥＸ－６１４Ｂ、エポキシ当量：１７３、１分子あたりのエポキシ基の数：３～４個）
ビスフェノールＡジグリシジルエーテル（三菱化学株式会社製、８２８、エポキシ当量：１８８、１分子あたりのエポキシ基の数：２個）
ソルビトールポリクロロヒドリン（合成例１、１分子あたりのハロヒドリン基の数：２～４個）
・（Ｂ）アミノ樹脂
メラミン樹脂（ＤＩＣ株式会社製、スーパーベッカミンＬ－１４５－６０、数平均分子量：１０７３、固形分濃度：５５％）
・アミン化合物
トリエチレンテトラミン（東京化成工業株式会社製、分子量：１４６）
・硬化促進剤
トルエンスルホン酸
・溶剤
トルエン（和光純薬工業株式会社製）
・樹脂基材
ポリエステル（ＰＥＴ）フィルム（東レ株式会社製、ルミラー、膜厚５０μｍ） (Materials used)
In the following examples and comparative examples, the following materials were used.
(A) Polyfunctional reactive compound sorbitol polyglycidyl ether (manufactured by Nagase ChemteX Corporation, Denacol EX-614B, epoxy equivalent: 173, number of epoxy groups per molecule: 3 to 4)
Bisphenol A diglycidyl ether (Mitsubishi Chemical Corporation, 828, epoxy equivalent: 188, number of epoxy groups per molecule: 2)
Sorbitol polychlorohydrin (Synthesis Example 1, number of halohydrin groups per molecule: 2 to 4)
(B) amino resin melamine resin (manufactured by DIC Corporation, Super Becamine L-145-60, number average molecular weight: 1073, solid content concentration: 55%)
・ Amine compound triethylenetetramine (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 146)
・ Hardening accelerator Toluenesulfonic acid ・ Solvent toluene (Wako Pure Chemical Industries, Ltd.)
-Resin-based polyester (PET) film (manufactured by Toray Industries Inc., Lumirror, film thickness 50 μm)
下記の実施例及び比較例においては、以下の材料を使用した。
・（Ａ）多官能反応性化合物
ソルビトールポリグリシジルエーテル（ナガセケムテックス株式会社製、デナコールＥＸ－６１４Ｂ、エポキシ当量：１７３、１分子あたりのエポキシ基の数：３～４個）
ビスフェノールＡジグリシジルエーテル（三菱化学株式会社製、８２８、エポキシ当量：１８８、１分子あたりのエポキシ基の数：２個）
ソルビトールポリクロロヒドリン（合成例１、１分子あたりのハロヒドリン基の数：２～４個）
・（Ｂ）アミノ樹脂
メラミン樹脂（ＤＩＣ株式会社製、スーパーベッカミンＬ－１４５－６０、数平均分子量：１０７３、固形分濃度：５５％）
・アミン化合物
トリエチレンテトラミン（東京化成工業株式会社製、分子量：１４６）
・硬化促進剤
トルエンスルホン酸
・溶剤
トルエン（和光純薬工業株式会社製）
・樹脂基材
ポリエステル（ＰＥＴ）フィルム（東レ株式会社製、ルミラー、膜厚５０μｍ） (Materials used)
In the following examples and comparative examples, the following materials were used.
(A) Polyfunctional reactive compound sorbitol polyglycidyl ether (manufactured by Nagase ChemteX Corporation, Denacol EX-614B, epoxy equivalent: 173, number of epoxy groups per molecule: 3 to 4)
Bisphenol A diglycidyl ether (Mitsubishi Chemical Corporation, 828, epoxy equivalent: 188, number of epoxy groups per molecule: 2)
Sorbitol polychlorohydrin (Synthesis Example 1, number of halohydrin groups per molecule: 2 to 4)
(B) amino resin melamine resin (manufactured by DIC Corporation, Super Becamine L-145-60, number average molecular weight: 1073, solid content concentration: 55%)
・ Amine compound triethylenetetramine (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 146)
・ Hardening accelerator Toluenesulfonic acid ・ Solvent toluene (Wako Pure Chemical Industries, Ltd.)
-Resin-based polyester (PET) film (manufactured by Toray Industries Inc., Lumirror, film thickness 50 μm)
（実施例１～３、比較例１～４）
下記表１に示す重量比で各成分を混合し、コーティング用樹脂組成物を得た。得られたコーティング用樹脂組成物を用いて後述する方法により貯蔵安定性の評価を行った。また、得られたコーティング用樹脂組成物を、バーコーター（Ｎｏ.２）を用いて樹脂基材上に塗布し、熱風乾燥機を用いて１３０℃で６０秒間加熱することにより硬化させて塗膜を形成し、部材を得た。部材を室温まで冷却させたものを試験片として用いて、後述する方法により速乾性、密着性及び耐薬品性の評価を行った。これらの結果を表１に示す。 (Examples 1 to 3, Comparative Examples 1 to 4)
Each component was mixed by the weight ratio shown in following Table 1, and the resin composition for coating was obtained. The storage stability was evaluated by the method described later using the obtained resin composition for coating. Further, the obtained coating resin composition is applied onto a resin substrate using a bar coater (No. 2), and cured by heating at 130 ° C. for 60 seconds using a hot air dryer to form a coating film. To obtain a member. Using the sample cooled to room temperature as a test piece, quick drying, adhesion and chemical resistance were evaluated by the methods described below. These results are shown in Table 1.
下記表１に示す重量比で各成分を混合し、コーティング用樹脂組成物を得た。得られたコーティング用樹脂組成物を用いて後述する方法により貯蔵安定性の評価を行った。また、得られたコーティング用樹脂組成物を、バーコーター（Ｎｏ.２）を用いて樹脂基材上に塗布し、熱風乾燥機を用いて１３０℃で６０秒間加熱することにより硬化させて塗膜を形成し、部材を得た。部材を室温まで冷却させたものを試験片として用いて、後述する方法により速乾性、密着性及び耐薬品性の評価を行った。これらの結果を表１に示す。 (Examples 1 to 3, Comparative Examples 1 to 4)
Each component was mixed by the weight ratio shown in following Table 1, and the resin composition for coating was obtained. The storage stability was evaluated by the method described later using the obtained resin composition for coating. Further, the obtained coating resin composition is applied onto a resin substrate using a bar coater (No. 2), and cured by heating at 130 ° C. for 60 seconds using a hot air dryer to form a coating film. To obtain a member. Using the sample cooled to room temperature as a test piece, quick drying, adhesion and chemical resistance were evaluated by the methods described below. These results are shown in Table 1.
（評価方法）
・貯蔵安定性
コーティング用樹脂組成物を２３ ℃条件下で静置して、濁りが発生するまでの時間を確認した。確認は最長で１２時間までとした。
・速乾性
作製直後の試験片の塗膜を指で触りタックの有無を確認し、下記の基準により２段階で評価した。
○：タック無し
×：タック有り
・密着性
作製直後の試験片の塗膜を指で１０回擦り、塗膜の剥離の有無を確認し、下記の基準により２段階で評価した。
○：剥離無し
×：剥離有り
・耐薬品性
作製直後の試験片を用いて耐薬品性試験を行った。具体的には、ラビングテスターを用いてメチルエチルケトンを染み込ませたガーゼを荷重３００ｇの条件で試験片の塗膜表面に押し当てた状態で３０回往復させてラビング試験を行い、塗膜の剥離の有無を確認し、下記の基準により２段階で評価した。
○：剥離無し
×：剥離有り (Evaluation methods)
-The resin composition for storage-stable coating was allowed to stand at 23 ° C, and the time until turbidity was confirmed was confirmed. Confirmation was up to 12 hours.
-The coating film of the test piece immediately after preparation of quick-drying was touched with a finger to confirm the presence or absence of tack, and evaluated in two stages according to the following criteria.
○: No tack x: Tacked / Adhesiveness The coating film of the test piece immediately after preparation of the specimen was rubbed 10 times with a finger to confirm the presence or absence of peeling of the coating film, and evaluated in two stages according to the following criteria.
○: No peeling ×: Peeling / chemical resistance A chemical resistance test was performed using a test piece immediately after preparation. Specifically, using a rubbing tester, the gauze impregnated with methyl ethyl ketone was reciprocated 30 times in a state where it was pressed against the coating surface of the test piece under the condition of a load of 300 g. And was evaluated in two stages according to the following criteria.
○: No peeling ×: With peeling
・貯蔵安定性
コーティング用樹脂組成物を２３ ℃条件下で静置して、濁りが発生するまでの時間を確認した。確認は最長で１２時間までとした。
・速乾性
作製直後の試験片の塗膜を指で触りタックの有無を確認し、下記の基準により２段階で評価した。
○：タック無し
×：タック有り
・密着性
作製直後の試験片の塗膜を指で１０回擦り、塗膜の剥離の有無を確認し、下記の基準により２段階で評価した。
○：剥離無し
×：剥離有り
・耐薬品性
作製直後の試験片を用いて耐薬品性試験を行った。具体的には、ラビングテスターを用いてメチルエチルケトンを染み込ませたガーゼを荷重３００ｇの条件で試験片の塗膜表面に押し当てた状態で３０回往復させてラビング試験を行い、塗膜の剥離の有無を確認し、下記の基準により２段階で評価した。
○：剥離無し
×：剥離有り (Evaluation methods)
-The resin composition for storage-stable coating was allowed to stand at 23 ° C, and the time until turbidity was confirmed was confirmed. Confirmation was up to 12 hours.
-The coating film of the test piece immediately after preparation of quick-drying was touched with a finger to confirm the presence or absence of tack, and evaluated in two stages according to the following criteria.
○: No tack x: Tacked / Adhesiveness The coating film of the test piece immediately after preparation of the specimen was rubbed 10 times with a finger to confirm the presence or absence of peeling of the coating film, and evaluated in two stages according to the following criteria.
○: No peeling ×: Peeling / chemical resistance A chemical resistance test was performed using a test piece immediately after preparation. Specifically, using a rubbing tester, the gauze impregnated with methyl ethyl ketone was reciprocated 30 times in a state where it was pressed against the coating surface of the test piece under the condition of a load of 300 g. And was evaluated in two stages according to the following criteria.
○: No peeling ×: With peeling
本発明のコーティング用樹脂組成物は１３０℃、６０秒という低温、短時間の乾燥条件であっても十分に乾燥させることが可能であり、その塗膜の密着性、耐薬品性も良好であった。一方、従来技術である比較例１～４では低温、短時間の乾燥条件では十分に乾燥させることができず、その結果として密着性、耐薬品性も不十分であった。
The coating resin composition of the present invention can be sufficiently dried even under low temperature and short drying conditions of 130 ° C. and 60 seconds, and the coating film has good adhesion and chemical resistance. It was. On the other hand, Comparative Examples 1 to 4 which are conventional techniques cannot be sufficiently dried under low temperature and short time drying conditions, and as a result, adhesion and chemical resistance are insufficient.
Claims (7)
- 樹脂基材に塗布するための組成物であって、
（Ａ）１分子中にエポキシ基及び／又はハロヒドリン基を２～１５個有する多官能反応性化合物、及び、
（Ｂ）数平均分子量２５０～１０，０００のアミノ樹脂
を含むことを特徴とするコーティング用樹脂組成物。 A composition for application to a resin substrate,
(A) a polyfunctional reactive compound having 2 to 15 epoxy groups and / or halohydrin groups in one molecule; and
(B) A coating resin composition comprising an amino resin having a number average molecular weight of 250 to 10,000. - （Ｂ）アミノ樹脂がメラミン樹脂である請求項１に記載のコーティング用樹脂組成物。 (B) The resin composition for coating according to claim 1, wherein the amino resin is a melamine resin.
- （Ｂ）成分の含有量が（Ａ）成分１００重量部に対して１０～１０，０００重量部である請求項１又は２に記載のコーティング用樹脂組成物。 The coating resin composition according to claim 1 or 2, wherein the content of the component (B) is 10 to 10,000 parts by weight with respect to 100 parts by weight of the component (A).
- （Ａ）多官能反応性化合物が１分子中にエポキシ基及び／又はハロヒドリン基を２～１０個有する請求項１～３のいずれか１項に記載のコーティング用樹脂組成物。 The coating resin composition according to any one of claims 1 to 3, wherein the polyfunctional reactive compound (A) has 2 to 10 epoxy groups and / or halohydrin groups in one molecule.
- 樹脂基材と、請求項１～４のいずれか１項に記載のコーティング用樹脂組成物を用いて樹脂基材上に形成された塗膜とを有することを特徴とする部材。 A member comprising a resin base material and a coating film formed on the resin base material using the coating resin composition according to any one of claims 1 to 4.
- 樹脂基材の材質がポリエステルである請求項５に記載の部材。 The member according to claim 5, wherein the resin base material is polyester.
- 請求項５又は６に記載の部材を製造するための方法であって、
請求項１～４のいずれか１項に記載のコーティング用樹脂組成物を樹脂基材の少なくとも一つの面に塗布する工程（１）、及び、
工程（１）で塗布したコーティング用樹脂組成物を６０～２５０℃で５～３００秒間加熱して硬化させる工程（２）
を含むことを特徴とする部材の製造方法。
A method for producing the member according to claim 5 or 6, comprising:
A step (1) of applying the coating resin composition according to any one of claims 1 to 4 to at least one surface of a resin substrate; and
Step (2) in which the coating resin composition applied in step (1) is cured by heating at 60 to 250 ° C. for 5 to 300 seconds.
The manufacturing method of the member characterized by including.
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| KR20220075758A (en) * | 2020-11-30 | 2022-06-08 | 주식회사 제일화성 | Biomass-based epoxy resin composition with excellent yellowing resistance |
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| CN113004242A (en) * | 2021-03-01 | 2021-06-22 | 中国林业科学研究院林产化学工业研究所 | Sorbitol-based aqueous cyclic carbonate, and preparation method and application thereof |
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| JP6874236B2 (en) | 2021-05-19 |
| CN108603071A (en) | 2018-09-28 |
| JPWO2017159732A1 (en) | 2019-01-24 |
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