WO2009110441A1 - 熱硬化性被膜用樹脂組成物 - Google Patents
熱硬化性被膜用樹脂組成物 Download PDFInfo
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- WO2009110441A1 WO2009110441A1 PCT/JP2009/053915 JP2009053915W WO2009110441A1 WO 2009110441 A1 WO2009110441 A1 WO 2009110441A1 JP 2009053915 W JP2009053915 W JP 2009053915W WO 2009110441 A1 WO2009110441 A1 WO 2009110441A1
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Definitions
- the present invention is used in fields where a high degree of cosmetics and excellent coating performance such as a coating film of an automobile body are required, such as scratch resistance, sulfite resistance, and excellent gloss characteristics during outdoor exposure.
- the present invention relates to a thermosetting coating composition that can be used and can be applied to plastics having a low heat distortion temperature.
- acrylic-melamine resins have been widely used as paints useful for automotive top coats and the like because of their excellent weather resistance and cosmetics.
- acrylic-melamine resins are inferior in sulfite resistance due to the use of melamine resin as a curing agent, and when this is applied to paints, it causes rain spots on the paint film due to acid rain, which reduces the appearance.
- thermosetting composition using an acid / epoxy curing system without using a melamine polymer has been proposed.
- JP-A-2002-179987 discloses a polyisocyanate which is a thermosetting system. Paints based on hydroxy-functional (meth) acrylate copolymers that are cross-linked are proposed. However, this paint has insufficient hardness, weather resistance and stain resistance. JP 2002-179987 A
- the object of the present invention is to use a conventional half-esterified copolymer, epoxy group and hydroxyl group by using what can form a specific acrylic thermosetting coating film as a resin component in the coating material constituting the coating film. While maintaining the sulfite resistance and weather resistance of the thermosetting composition containing the compound having the above, it is more resistant to scratches and cosmetics, particularly weather resistance than conventional UV curing systems, silicone coatings, and urethane acrylic thermosetting coatings. Another object of the present invention is to provide a thermosetting coating resin composition that forms a coating film having excellent scratch resistance and stain resistance after a property test.
- the first gist of the present invention is a monomer (a) unit represented by the following formula (1): A secondary hydroxyl group-containing polyoxyalkylene mono (meth) acrylate monomer (b) unit and an isobornyl (meth) acrylate monomer (c) unit, and the content of the monomer (a) unit ( Acrylic copolymer for thermosetting coating resin composition (A) having a mass) greater than the content of the monomer (b) unit (In the formula (1), R represents a hydrogen atom or a methyl group, m is an integer of 0 to 2, n is an integer of 1 to 3, and the sum of m and n is 1 to 3.) [2] A second gist of the present invention is a thermosetting coating resin composition containing the acrylic copolymer (A) and a polyisocyanate curing agent (B). [3] A third aspect of the present invention is a coating film obtained by curing the thermosetting film resin composition according to [2]. [4] A fourth aspect of the first aspect
- (meth) acryl is a general term for acrylic and methacrylic.
- thermosetting coatings of the present invention When the resin composition for thermosetting coatings of the present invention is used, appearance, (initial, after weather resistance) scratch resistance, appearance finish, weather resistance, storage stability, stain resistance, curability, hardness, sulfite resistance It is possible to provide an excellent coating film, which is very useful industrially.
- Examples of the monomer that polymerizes to give a (meth) acrylate monomer (a) unit include, for example, 2-hydroxypropyl (meth) acrylate, 2- Hydroxybutyl (meth) acrylate etc. are mentioned, These can be used individually or in combination of 2 or more types. It is important that the alkyl group in the ester moiety of the monomer (a) unit has 2 to 4 carbon atoms and has a secondary hydroxyl group. This is because when the carbon number of the alkyl group is 5 or more, the coating film appearance and pot life are lowered.
- bonded with the said alkyl group is primary, or when the carbon number of the said alkyl group is 1, it is because a finished external appearance will fall.
- the reason for this is considered to be the difference in curing rate between the primary hydroxyl group and the secondary hydroxyl group.
- a clear coat layer is formed before the base coat layer is solidified.
- the content (mass) of the monomer (a) unit is the secondary hydroxyl group-containing polyoxyalkylene mono (meth) acrylate monomer (b) unit (hereinafter referred to as the monomer (b) unit). It is important that the content is greater than This is because the monomer (b) unit has an effect of imparting scratch resistance, but has high hydrophilicity, and if it is more than the monomer (a) unit, the stain resistance becomes insufficient. Moreover, when there is much content of a monomer (b) unit, the molecular weight between bridge
- the content of the monomer (a) unit is preferably 10 to 50% by mass and more preferably 10 to 35% by mass with respect to the acrylic copolymer (A). This is because if it is less than 10% by mass, the curability and hardness are insufficient, and if it exceeds 50% by mass, the initial scratch resistance and the scratch resistance after the weather resistance test are insufficient.
- the monomer (a) unit and primary hydroxyl group-containing (meth) acrylate may be used in combination, the amount of primary hydroxyl group-containing (meth) acrylate used is an acrylic copolymer in order to suppress deterioration of the appearance. Less than 15 mass% is preferable with respect to a polymer (A).
- the content of each monomer unit in the acrylic copolymer (A) can be quantified by NMR, gas chromatograph or the like.
- Examples of the secondary hydroxyl group-containing polyoxyalkylene mono (meth) acrylate that gives a monomer (b) unit by polymerization include a reaction product of polyalkylene glycol and (meth) acrylate. Specifically, it has the following general formula.
- R1 is a hydrogen atom or a methyl group
- n, m and l are each independently an integer of 0 to 10, and at least one of n, m and l is 1 or more.
- Oxyalkylene structures include not only block copolymers but also random copolymers.
- those having a polypropylene glycol moiety where m is preferably 1 or more are preferred.
- Specific examples include “Blemmer” made by Nippon Oils and Fats shown below. The parentheses indicate the correspondence with the formula (2).
- the monomer (b) unit has a secondary hydroxyl group in order to appropriately control the curing rate to improve the appearance of the coating film.
- the content of the monomer (b) unit is preferably 5 to 35% by mass and more preferably 5 to 25% by mass with respect to the acrylic copolymer (A). This is because if it is less than 5% by mass, the initial scratch resistance and scratch resistance after the weather resistance test will be insufficient, and if it exceeds 35% by mass, the curability and stain resistance will be insufficient.
- the acrylic copolymer (A) contains an isobornyl (meth) acrylate monomer (c) unit (hereinafter also referred to as a monomer (c) unit), thereby improving initial scratch resistance, A reduction in scratch resistance after the weather resistance test can be prevented.
- the content of the monomer (c) unit is preferably 10 to 50% by mass with respect to the acrylic copolymer (A). If it is less than 10% by mass, the hardness and stain resistance will be low, and if it exceeds 50% by mass, the coating film hardness will be too high and the scratch resistance will be reduced.
- the acrylic copolymer (A) includes a monomer unit (d) derived from an ethylenically unsaturated monomer other than the above-mentioned monomer (a) unit to (c) unit (hereinafter referred to as monomer).
- (D) also referred to as a unit
- monomer ethylenically unsaturated monomer which superposes
- the ethylenically unsaturated monomer which has a carboxyl group can be mentioned.
- Examples include methacrylic acid, acrylic acid, fumaric acid, itaconic acid, maleic acid, crotonic acid, vinyl benzoic acid, maleic acid monobutyl ester, itaconic acid monomethyl ester, and itaconic acid butyl ester. It can also be used in combination of more than one species.
- Examples of ethylenically unsaturated monomers other than those having a carboxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, i -Butyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth)
- the content of the monomer (d) unit is a value obtained by subtracting the total content of the monomer (a) unit to the (c) unit from the acrylic copolymer (A), and is 5 to 50% by mass. preferable.
- the acrylic copolymer (A) preferably has a hydroxyl value in the range of 130 to 180 mgKOH / g, more preferably in the range of 135 to 175 mgKOH / g. This is because when the hydroxyl value of the acrylic copolymer (A) is less than 130 mgKOH / g, the hardness and scratch resistance of the cured coating film tend to decrease, and when it exceeds 180 mgKOH / g, This is because the water resistance and impact resistance tend to decrease.
- the acid value of the acrylic copolymer (A) is preferably in the range of 1 to 30 mgKOH / g. This is because if the acid value is less than 1 mgKOH / g, the curability and hardness are lowered, and if it is greater than 30 mgKOH / g, the appearance tends to be lowered.
- the mass average molecular weight of the acrylic copolymer (A) is preferably 2000 to 50000. If the mass average molecular weight is less than 2000, the solvent resistance, hardness, and weather resistance of the formed coating film tend to decrease, and if it exceeds 50,000, the cosmetic properties and solvent volatility during coating decrease. It is because it is in a tendency.
- the acrylic copolymer (A) of the present invention is obtained by polymerizing monomers that give monomers (a) to (d) units by solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, etc. These can be produced by known polymerization methods. For example, when the acrylic copolymer (A) is produced by a solution polymerization method, the monomer is copolymerized in the presence of an organic solvent and a polymerization initiator.
- the polymerization initiator can be selected from commonly used polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide and the like. Further, chain transfer agents such as 2-mercaptoethanol and n-octyl mercaptan can be used as necessary.
- the acrylic copolymer (A) of the present invention can be used as a thermosetting coating resin composition together with a polyisocyanate curing agent (B).
- the polyisocyanate curing agent (B) is not particularly limited and can be appropriately selected according to the use.
- aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate
- isophorone examples thereof include alicyclic diisocyanates such as diisocyanate and 4,4′-methylenebis (cyclohexyl isocyanate), and aromatic diisocyanates such as xylylene diisocyanate and tolylene diisocyanate.
- polyisocyanate curing agent (B) low molecular weight polyester resins having functional groups that react with polyhydric alcohols such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and isocyanate groups, and isocyanate groups and water Or a polymer of a buret body or a diisocyanate, and a polyisocyanate curing agent (B) and a blocked with a known blocking agent such as a lower monohydric alcohol or methyl ethyl ketoxime can be used in combination.
- polyhydric alcohols such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and isocyanate groups
- a polymer of a buret body or a diisocyanate and a polyisocyanate curing agent (B) and a blocked with a known blocking agent such as a lower monohydric alcohol or
- thermosetting coating resin composition a curing accelerator represented by dibutyltin dilaurate or the like, or a curing catalyst (amine-based etc.) can be used as necessary.
- thermosetting coating resin composition of the present invention when the thermosetting coating resin composition of the present invention is made into a paint, inorganic pigments such as titanium oxide, organic pigments such as cyanine blue, surface preparation agents, ultraviolet absorbers, light stabilizers, oxidation agents Additives such as an inhibitor and an anti-sagging agent are blended as necessary using known means, and finally diluted with an organic solvent for dilution so as to have an appropriate viscosity.
- organic solvent for dilution include xylene, Solvesso # 100, Solvesso # 150 (Esso aromatic petroleum derivative), 2-heptanone ketone (Eastman), and ester solvent EEP (Eastman) And propylene glycol monomethyl ether acetate.
- the resin composition for a thermosetting film of the present invention can be used as a clear coat layer of a multilayer coating film.
- the clear coat layer includes a single-layer clear coat layer composed only of the thermosetting coating resin composition of the present invention or a known thermosetting coating resin composition, preferably a clear coating layer composed of a thermosetting acrylic resin. Any of the multi-layer clear coat layers may be used, and these can be appropriately selected depending on the application.
- thermosetting coating resin composition of the present invention can be applied by spray coating, brush coating, dip coating, roll coating, flow coating, or the like.
- the clear coating composition of the invention can be advantageously used for wood, metal, glass, cloth, plastic, foam, etc., particularly plastic and metal surfaces (for example, steel, aluminum and alloys thereof). It can be suitably used as a paint.
- part means part by mass.
- ⁇ Adjustment of base coat paint (D-1)> In the aqueous base copolymer coating aqueous solution (C-1), 45 parts of melamine curing agent Cymel 703 (manufactured by Nippon Cytec Industries, methylated melamine resin, 80%), 20 parts of aluminum paste # 9660 (manufactured by Toyo Aluminum), 10 parts of a phosphoric acid-containing resin and 30 parts of isopropyl alcohol were mixed. 4 was diluted with water until the viscosity reached 40 seconds.
- the physical properties of the acrylic copolymer were evaluated as follows.
- RSAII viscoelasticity analyzer
- Mc (molecular weight between crosslinks) 3 fRT / E ′
- R gas constant
- f density of sample coating film ⁇ hardness>
- An automotive cationic electrodeposition coating was applied to a zinc phosphate-treated steel plate (30 cm ⁇ 45 cm) and baked at 180 ° C. for 30 minutes. Further, an aminoalkyd resin-based intermediate coating was applied and baked at 160 ° C. for 30 minutes, and then the coating film was wet-polished and dried. First, the base coat paint (D-1) was spray-coated on the coating film so as to have a dry film thickness of 10 to 50 ⁇ m, allowed to stand for 5 minutes, and then preheated at 80 ° C. for 10 minutes.
- the clear coat paints (B-1) to (B-5) are repeatedly applied by a wet-on-wet method so that the dry film thickness becomes 30 to 40 ⁇ m, and left for 10 minutes, then at 140 ° C.
- a test plate on which a coating film was formed was baked for 30 minutes with a hot air dryer. Using this test plate, the hardest hardness without scratches was determined by scratching the coating film at an angle of 45 degrees using a Mitsubishi pencil “Uni”.
- a coating film was formed in the same manner as the hardness measurement, and the finished appearance was measured using Wave-scan-DOI (BYK-Gardner).
- Wc value corresponds to the items of dust and mud of the appearance of the coating film
- Wd correlates to the items of skin and dust of the appearance.
- Appearance evaluation was performed using Wc and Wd values. These values are better as the numerical value is smaller.
- a test plate was prepared in the same manner as the hardness measurement. Using a friction fastness tester manufactured by Daiei Kagaku Seiki Co., Ltd., apply gauze coated with a 50% aqueous solution of Maken Cleanser manufactured by Maken Soap Co., Ltd. to the part that comes into contact with the coated surface, and perform 50 reciprocating friction tests at a load of 1 kg. The scar was visually determined.
- a test plate was prepared in the same manner as the hardness measurement, and evaluated using the sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.) on the basis of the gloss value after 2000 hours with respect to the initial gloss value.
- thermosetting film resin composition of the present invention when used, appearance, (initial, after weather resistance) scratch resistance, appearance finish It is possible to provide a coating film having excellent properties, weather resistance, storage stability, stain resistance, curability, hardness, and sulfite resistance, which is very useful industrially.
- Comparative Example 1 was an example using 2-hydroxyethyl methacrylate units instead of the monomer (a) units, and the appearance was deteriorated.
- Comparative Example 2 is an example in which the content of the monomer (b) unit is larger than the content of the monomer (a) unit, and the appearance, hardness and stain resistance are deteriorated.
- Comparative Example 3 a cyclohexyl methacrylate unit was used instead of the monomer (c) unit, and the scratch resistance and stain resistance after the initial and weather resistance tests deteriorated.
- thermosetting coatings of the present invention When the resin composition for thermosetting coatings of the present invention is used, appearance, (initial, after weather resistance) scratch resistance, appearance finish, weather resistance, storage stability, stain resistance, curability, hardness, sulfite resistance Excellent coatings are available and are very useful industrially.
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- Engineering & Computer Science (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
Description
本願は、2008年3月6日に、日本に出願された特願2008-56545号に基づき優先権を主張し、その内容をここに援用する。
第2級水酸基含有ポリオキシアルキレンモノ(メタ)アクリレート単量体(b)単位、及びイソボルニル(メタ)アクリレート単量体(c)単位を含有し、前記単量体(a)単位の含有量(質量)が前記単量体(b)単位の含有量よりも大きい熱硬化性被覆用樹脂組成物用アクリル系共重合体(A)
[2] 本発明の第2の要旨は、前記アクリル系共重合体(A)と、ポリイソシアネート硬化剤(B)とを含有する熱硬化性被覆用樹脂組成物である。
[3] 本発明の第3の要旨は、[2]に記載の熱硬化性被膜用樹脂組成物を硬化させて得られる塗膜。
[4] 本発明の第4の要旨は、[3]に記載の塗膜を有する物品。
上記式(2)で表されるポリアルキレングリコール(メタ)アクリレートのうち、好ましくはmが1以上のポリプロピレングリコール部位を持つものである。具体的には以下に示す日本油脂製「ブレンマー」が挙げられる。なお、括弧内は式(2)との対応を示す。
単量体(b)単位の含有量はアクリル系共重合体(A)に対し、5~35質量%が好ましく、5~25質量%がより好ましい。これは5質量%未満では初期耐擦り傷性、耐候性試験後耐擦り傷性が不十分になり、35質量%を超えると、硬化性、耐汚染性が不十分となるためである。
攪拌翼、原料供給ライン、窒素加圧ライン、温調装置を備えた攪拌槽型反応装置に溶剤としてソルベッソ#150(エッソ社製、芳香族炭化水素)を45部仕込み、系内に窒素を100ml/分で吹き込みながら釜内温を150℃まで加熱した。
アクリル系共重合体溶液(A-1)に、ポリイソシアネート硬化剤として、NCO基当量の比がOH/NCO=1/1になるようにソルベッソ#100にて50%まで希釈したデュラネートTPA-100(旭化成製、NCO比率23.1質量%)を所定量加え、モダフロー(モンサット社製、表面調整剤)0.08部、チヌビン900(チバガイギー社製、紫外線吸収剤)1部、サノール292(三共(株)製、光安定剤)1部を加え、希釈シンナー(ソルベッソ#100/ソルベッソ#150=1/1)によって、フォードカップNo.4にて20秒の粘度になるまで希釈調整してクリヤーコート塗料(B-1)を得た。
攪拌翼、原料供給ライン、窒素加圧ライン、温調装置を備えた攪拌槽型反応装置に溶剤としてブチセロソルブを45部仕込み、系内に窒素を100ml/分で吹き込みながら釜内温を100℃まで加熱した。次に、
スチレン 30部
メチルメタクリレート 15部
n-ブチルアクリレート 34部
2-エチルヘキシルメタクリレート 6部
2-ヒドロキシメタクリレート 12部
メタクリル酸 3部
アゾビスイソブチロニトリル 1部
からなる単量体と重合開始剤の混合物を準備し、滴下ポンプにて容器上部より4時間かけて連続的に滴下した。滴下終了後、内温を90℃まで下げ、追加触媒としてアゾビスイソブチロニトリル0.5部をブチルセロソルブ5部に溶解させたものを30分かけて連続的に滴下し、同温度にて30分保持した後、更に80℃まで降温し、ジメチルアミノエタノールを加えることで全カルボキシル基の80モル%を中和してベースコート塗料用系共重合体水溶液(C-1)を得た。
ベースコート塗料用系共重合体水溶液(C-1)に、メラミン硬化剤のサイメル703(日本サイテックインダストリーズ製、メチル化メラミン樹脂、80%)45部、アルミペースト#9670(東洋アルミニウム製)20部、リン酸含有樹脂10部およびイソプロピルアルコール30部を混合し、さらにフォードカップNo.4にて40秒の粘度になるまで水を加えて希釈した。
1gのアクリル系共重合体溶液をアルミ皿上にサンプリングし、150℃で1時間乾燥させたときの不揮発分の比率(質量%)を求めた。
アクリル系共重合体溶液のテトラヒドロフラン溶液(0.4質量%)を調整後、TOSO社製カラム(GE4000HXL及びG2000HXL)が装着されたTOSO社製ゲルパーミエーションクロマトグラフィー装置に上記の溶液100μlを注入し、流量:1ml/分、溶離液:テトラヒドロフラン、カラム温度:40℃の条件でゲルパーミエーションクロマトグラフィー法を用いて測定され、標準ポリスチレンで換算された値を求めた。
硬化性は架橋間分子量により判断した。架橋間分子量は以下の方法で求めた。
R:気体定数 f:試料塗膜の密度
<硬度>
リン酸亜鉛処理された鋼板(30cm×45cm)に自動車用カチオン電着塗料を塗装し、180℃で30分間焼き付けた。さらにアミノアルキッド樹脂系の中塗り塗料を塗装し、160℃で30分間焼き付けた後、塗膜を水研し、乾燥させた。この塗膜上にまず、ベースコート塗料(D-1)を乾燥膜厚が10~50μmとなるようにスプレー塗装し、5分間放置した後、80℃で10分間プレヒートした。次に塗板を冷却した後、クリヤーコート塗料(B-1)~(B-5)を乾燥膜厚が30~40μmとなるようにウェットオンウエット方式で重ね塗り、10分間放置後、140℃の熱風乾燥機で30分間焼き付けて塗膜が形成された試験板を作製した。この試験板により、三菱鉛筆「ユニ」を用いて45度の角度で塗膜を引っかいて傷のつかない最も硬い硬度を判定した。
硬度測定と同様に塗膜を形成し、Wave-scan-DOI(BYK-Gardner社製)を用いて仕上がり外観を測定した。測定値のうちWc値は塗膜外観のチリ、ムジの項目に該当し、Wdは外観の肌、チリの項目に相関する。外観評価はWc、Wd値を用いて行った。これらの値は、数値が小さいほど良好である。
硬度測定と同様に試験板を作製した。大栄科学精器(株)製の摩擦堅牢度試験機を用い、マケン石鹸(株)製マケンクレンザーの50%水溶液を塗りつけたガーゼを塗面と接触する箇所に当て、荷重1kgで50往復摩擦試験を行い、傷跡を目視判定した。
△:若干傷はあるが使用可能
×:傷が多く、不良
<耐候性>
硬度測定と同様に試験板を作製し、サンシャインウェザオメーター(スガ試験機製)を用い、初期光沢値に対する2000時間後の光沢値を基に以下の基準で評価した。
△:光沢不良
×:光沢不良、マイクロクラック有
<耐候性試験後耐擦り傷性>
上記耐候性試験を実施した塗膜にて、大栄科学精器(株)製の摩擦堅牢度試験機を用い、マケン石鹸(株)製マケンクレンザーの50%水溶液を塗りつけたガーゼを塗面と接触する箇所に当て、荷重1kgで50往復摩擦試験を行い、傷跡を目視判定した。
△:若干傷はあるが使用可能
<耐汚染性>
硬度測定と同様に試験板を作製し、屋外に設置し3ヶ月経過後における水シミの有無を目視判定した。
×:水シミあり
以上の実施例からも明らかなように、本発明の熱硬化性被膜用樹脂組成物を用いると、外観、(初期、耐候後)耐擦り傷性、外観仕上がり性、耐候性、貯蔵安定性、耐汚染性、硬化性、硬度、耐亜硫酸性の優れた塗膜の提供が可能であり、工業上非常に有益なものである。
Claims (4)
- 請求項1記載のアクリル系共重合体(A)と、ポリイソシアネート硬化剤(B)とを含有する熱硬化性被覆用樹脂組成物。
- 請求項2に記載の熱硬化性被膜用樹脂組成物を硬化させて得られる塗膜。
- 請求項3に記載の塗膜を有する物品。
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CN2009801073539A CN101959910A (zh) | 2008-03-06 | 2009-03-03 | 热固性被膜用树脂组合物 |
JP2009514568A JP5604870B2 (ja) | 2008-03-06 | 2009-03-03 | 熱硬化性被膜用樹脂組成物 |
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Cited By (2)
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JP2011068864A (ja) * | 2009-08-31 | 2011-04-07 | Kansai Paint Co Ltd | 塗料組成物及び塗膜形成方法 |
WO2022215877A1 (ko) * | 2021-04-05 | 2022-10-13 | 삼성디스플레이주식회사 | 점착 조성물 및 이를 포함한 디스플레이 장치 |
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CN105384884B (zh) * | 2015-12-04 | 2018-10-12 | 湖北航天化学技术研究所 | 一种可化学降解推进剂固化促进剂的合成方法 |
CN112708317A (zh) * | 2021-01-15 | 2021-04-27 | 江阴市荣新塑化有限公司 | 一种汽车铝制材料喷涂用高耐磨耐候面漆及其制备方法 |
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- 2009-03-03 WO PCT/JP2009/053915 patent/WO2009110441A1/ja active Application Filing
- 2009-03-03 CN CN2009801073539A patent/CN101959910A/zh active Pending
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CN101959910A (zh) | 2011-01-26 |
JPWO2009110441A1 (ja) | 2011-07-14 |
JP5604870B2 (ja) | 2014-10-15 |
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