JP2020139055A - Aqueous composition, coating film, and method for producing aqueous composition - Google Patents
Aqueous composition, coating film, and method for producing aqueous composition Download PDFInfo
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- JP2020139055A JP2020139055A JP2019035667A JP2019035667A JP2020139055A JP 2020139055 A JP2020139055 A JP 2020139055A JP 2019035667 A JP2019035667 A JP 2019035667A JP 2019035667 A JP2019035667 A JP 2019035667A JP 2020139055 A JP2020139055 A JP 2020139055A
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- aqueous composition
- monomer unit
- copolymer
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- 239000000203 mixture Substances 0.000 title claims abstract description 83
- 239000011248 coating agent Substances 0.000 title claims abstract description 34
- 238000000576 coating method Methods 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 41
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 180
- 238000006116 polymerization reaction Methods 0.000 claims description 44
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 125000001931 aliphatic group Chemical group 0.000 claims description 20
- 150000001993 dienes Chemical class 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 239000012948 isocyanate Substances 0.000 claims description 15
- 150000002513 isocyanates Chemical class 0.000 claims description 15
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 239000004566 building material Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 37
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 57
- -1 2-hydroxypropyl Chemical group 0.000 description 37
- 239000002994 raw material Substances 0.000 description 26
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- 239000003505 polymerization initiator Substances 0.000 description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000003431 cross linking reagent Substances 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
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- 150000001875 compounds Chemical class 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
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- 239000000654 additive Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 239000007870 radical polymerization initiator Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
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- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
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- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- KMHZPJNVPCAUMN-UHFFFAOYSA-N Erbon Chemical compound CC(Cl)(Cl)C(=O)OCCOC1=CC(Cl)=C(Cl)C=C1Cl KMHZPJNVPCAUMN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
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- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- 239000003607 modifier Substances 0.000 description 2
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 description 2
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- 239000005056 polyisocyanate Substances 0.000 description 2
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、水系組成物、塗膜、及び水系組成物の製造方法に関する。 The present invention relates to an aqueous composition, a coating film, and a method for producing an aqueous composition.
スチレン・ブタジエン系共重合体ラテックス等のラテックスは、塗工紙のバインダー、カーペットの裏打ちバインダー、各種接着剤及び塗料原料に幅広く使用されている。近年、その機械的安定性及び化学的安定性の向上などを目的として、酸性官能基、水酸基を含有する単量体をラテックスの共重合体成分として、少量配合させることによって得られる変性ラテックスが広く普及している（例えば、特許文献１及び２）。 Latexes such as styrene-butadiene copolymer latex are widely used in coated paper binders, carpet lining binders, various adhesives, and paint raw materials. In recent years, for the purpose of improving its mechanical stability and chemical stability, modified latex obtained by blending a monomer containing an acidic functional group and a hydroxyl group as a copolymer component of latex in a small amount has been widely used. It is widely used (for example, Patent Documents 1 and 2).
しかしながら、耐水性能に関し、特に湿潤環境における耐久性を求められる建築分野においては、耐水性が更に向上した塗膜の開発が求められていた。
本発明は、耐水性に優れた塗膜を形成する水系組成物、塗膜、及び水系組成物の製造方法を提供することを目的とする。
However, with regard to water resistance, especially in the construction field where durability in a moist environment is required, development of a coating film having further improved water resistance has been required.
An object of the present invention is to provide a water-based composition, a coating film, and a method for producing a water-based composition for forming a coating film having excellent water resistance.
本発明者らは、上記課題を解決するために鋭意検討した結果、イソシアネート系硬化剤と混合した後に所定の粘度となる水系組成物が、耐水性に優れた塗膜を形成できることを見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the present inventors have found that an aqueous composition having a predetermined viscosity after being mixed with an isocyanate-based curing agent can form a coating film having excellent water resistance. The invention was completed.
すなわち、本発明は、以下の通りである。
［１］
共重合体を含む、水系組成物であって、
前記水系組成物と炭酸カルシウムとポリビニルアルコールとの混合物に、ジフェニルメタン−４，４’−ジイソシアネートを添加し３０分放置した後の粘度が、添加直後の粘度の５．８倍以下となる、前記水系組成物。
［２］
前記共重合体が、前記共重合体を構成する単量体単位の総量を１００質量部とした場合、
１０質量部以上３５質量部以下の水酸基含有不飽和単量体単位（Ａ）、
１０質量部以上６５質量部以下の脂肪族共役ジエン系単量体単位（Ｂ）、及び
０質量部以上７５質量部以下の重合性不飽和単量体単位（Ｃ）、
を有し、
前記重合性不飽和単量体単位（Ｃ）が、前記水酸基含有不飽和単量体単位（Ａ）及び前記脂肪族共役ジエン系単量体単位（Ｂ）と異なる、
［１］に記載の水系組成物。
［３］
前記重合性不飽和単量体単位（Ｃ）が、前記共重合体を構成する単量体単位の総量を１００質量部とした場合、０．０１質量部以上０．１質量部以下の酸性官能基含有不飽和単量体単位を含む、［２］に記載の水系組成物。
［４］
イソシアネート系硬化剤を更に含む、［１］〜［３］のいずれかに記載の水系組成物。
［５］
前記共重合体の平均粒子径が、１５０ｎｍ〜２５０ｎｍである、［１］〜［４］のいずれかに記載の水系組成物。
［６］
［１］〜［５］のいずれかに記載の水系組成物の硬化物からなる塗膜。
［７］
建築材料用である［６］記載の塗膜。
［８］
［１］〜［５］のいずれかに記載の水系組成物の製造方法であって、
水酸基含有不飽和単量体及び脂肪族共役ジエン系単量体を重合する重合工程を含み、
前記重合工程を実施する前に、前記製造方法で使用される水酸基含有不飽和単量体の全量が前記脂肪族共役ジエン系単量体と混合される、前記製造方法。
That is, the present invention is as follows.
[1]
An aqueous composition containing a copolymer.
The viscosity of the mixture of the aqueous composition, calcium carbonate and polyvinyl alcohol after adding diphenylmethane-4,4'-diisocyanate and leaving it for 30 minutes is 5.8 times or less the viscosity immediately after the addition. Composition.
[2]
When the total amount of the monomer units constituting the copolymer is 100 parts by mass, the copolymer
Hydroxy group-containing unsaturated monomer unit (A) of 10 parts by mass or more and 35 parts by mass or less,
Aliphatic conjugated diene monomer unit (B) of 10 parts by mass or more and 65 parts by mass or less, and polymerizable unsaturated monomer unit (C) of 0 parts by mass or more and 75 parts by mass or less.
Have,
The polymerizable unsaturated monomer unit (C) is different from the hydroxyl group-containing unsaturated monomer unit (A) and the aliphatic conjugated diene-based monomer unit (B).
The aqueous composition according to [1].
[3]
The acidic functional of the polymerizable unsaturated monomer unit (C) is 0.01 parts by mass or more and 0.1 parts by mass or less when the total amount of the monomer units constituting the copolymer is 100 parts by mass. The aqueous composition according to [2], which contains a group-containing unsaturated monomer unit.
[4]
The aqueous composition according to any one of [1] to [3], further comprising an isocyanate-based curing agent.
[5]
The aqueous composition according to any one of [1] to [4], wherein the average particle size of the copolymer is 150 nm to 250 nm.
[6]
A coating film made of a cured product of the aqueous composition according to any one of [1] to [5].
[7]
The coating film according to [6], which is used for building materials.
[8]
The method for producing an aqueous composition according to any one of [1] to [5].
Including a polymerization step of polymerizing a hydroxyl group-containing unsaturated monomer and an aliphatic conjugated diene-based monomer.
The production method, wherein the total amount of the hydroxyl group-containing unsaturated monomer used in the production method is mixed with the aliphatic conjugated diene-based monomer before carrying out the polymerization step.
本発明によれば、耐水性に優れた塗膜を形成する水系組成物、塗膜、及び水系組成物の製造方法を提供することができる。 According to the present invention, it is possible to provide a water-based composition, a coating film, and a method for producing a water-based composition that forms a coating film having excellent water resistance.
以下に本発明を実施するための形態（以下、「本実施形態」という。）について詳細に説明するが、本発明はこれに限定されるものではなく、その要旨を逸脱しない範囲で様々な変形が可能である。 Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail, but the present invention is not limited thereto, and various modifications are made without departing from the gist thereof. Is possible.
本明細書において、「単量体」は、共重合体を形成するための原料を意味する。なお、単に「単量体」と記載する場合、「単量体」は共重合体を形成するための全ての種類の単量体を包含する。 As used herein, the term "monomer" means a raw material for forming a copolymer. When simply referred to as "monomer", "monomer" includes all kinds of monomers for forming a copolymer.
本明細書において、「単量体単位」は、共重合体の一部を構成する、単量体に由来する構造単位を意味する。なお、単に「単量体単位」と記載する場合、「単量体単位」は共重合体を構成する全ての種類の構造単位を包含する。 As used herein, the term "monomer unit" means a structural unit derived from a monomer that constitutes a part of a copolymer. When simply described as a "monomer unit", the "monomer unit" includes all kinds of structural units constituting the copolymer.
本明細書において、「（メタ）アクリレート」は、メタアクリレート及びアクリレートの双方を包含する。 As used herein, "(meth) acrylate" includes both methacrylate and acrylate.
［水系組成物］
本実施形態は、共重合体を含む、水系組成物であって、前記水系組成物と炭酸カルシウムとポリビニルアルコールとの混合物に、ジフェニルメタン−４，４’−ジイソシアネートを添加し３０分放置した後の粘度が、添加直後の粘度の５．８倍以下となる、前記水系組成物に関する。
[Aqueous composition]
This embodiment is an aqueous composition containing a copolymer, and after adding diphenylmethane-4,4'-diisocyanate to a mixture of the aqueous composition, calcium carbonate and polyvinyl alcohol and leaving it for 30 minutes. The present invention relates to the aqueous composition having a viscosity of 5.8 times or less the viscosity immediately after addition.
本明細書において、「水系組成物」とは、水を含む組成物であって、組成物中で水が連続相を形成している組成物である。水系組成物の水以外の成分は、組成物中で分散相を形成していてもよいし、水中に溶解していてもよい。水の含有量は、特に限定されないが、水系組成物を基準として、２０質量％以上９０質量％以下、３０質量％以上８０質量％以下、４０質量％以上７０質量％以下等としてもよい。 In the present specification, the "aqueous composition" is a composition containing water, in which water forms a continuous phase in the composition. The components of the aqueous composition other than water may form a dispersed phase in the composition or may be dissolved in water. The content of water is not particularly limited, but may be 20% by mass or more and 90% by mass or less, 30% by mass or more and 80% by mass or less, 40% by mass or more and 70% by mass or less, based on the aqueous composition.
本実施形態の水系組成物は、例えば、塗工紙のバインダー、カーペットの裏打ちバインダー、各種接着剤、塗料、及びモルタル混和剤の原料に好適に用いることができる。 The aqueous composition of the present embodiment can be suitably used as a raw material for, for example, a binder for coated paper, a binder for lining carpet, various adhesives, paints, and a mortar admixture.
本実施形態の共重合体は、以下で説明する単量体単位を有することができる。 The copolymer of the present embodiment can have a monomer unit described below.
＜水酸基含有不飽和単量体単位（Ａ）＞
本実施形態の共重合体は、耐水性を向上させる観点から、水酸基含有不飽和単量体単位（Ａ）を有することが好ましい。
本実施形態の水酸基含有不飽和単量体単位（Ａ）としては、特に限定されないが、例えば、２−ヒドロキシエチル（メタ）アクリレートなどのヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレートなどのヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレートなどのヒドロキシブチル（メタ）アクリレート、３−クロロ−２−ヒドロキシプロピル（メタ）アクリレート、ジ−（エチレングリコール）マレエート、ジ−（エチレングリコール）イタコネート、２−ヒドロキシエチルマレエート、ビス（２−ヒドロキシエチル）マレエート、及び２−ヒドロキシエチルメチルフマレートからなる群より選ばれる１種以上の水酸基含有不飽和単量体に由来する単位が挙げられる。
これらの中でも、耐水性を一層向上できる観点から、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、及びヒドロキシブチル（メタ）アクリレートからなる群より選ばれる１種以上の水酸基含有不飽和単量体に由来する単位が好ましく、ヒドロキエチル（メタ）アクリレート及びヒドロキシプロピル（メタ）アクリレートからなる群より選ばれる１種以上の水酸基含有不飽和単量体に由来する単位がより好ましい。
なお、水酸基含有不飽和単量体単位（Ａ）の原料となる水酸基含有不飽和単量体を以下、「原料成分（ａ）」と記載することがある。
<Hydroxy group-containing unsaturated monomer unit (A)>
The copolymer of the present embodiment preferably has a hydroxyl group-containing unsaturated monomer unit (A) from the viewpoint of improving water resistance.
The hydroxyl group-containing unsaturated monomer unit (A) of the present embodiment is not particularly limited, and is, for example, hydroxyethyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate. Hydroxypropyl (meth) acrylate such as 2-hydroxybutyl (meth) acrylate, hydroxybutyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di- Contains one or more hydroxyl groups selected from the group consisting of (ethylene glycol) maleate, di- (ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis (2-hydroxyethyl) maleate, and 2-hydroxyethyl methyl fumarate. Examples include units derived from unsaturated monomers.
Among these, one or more hydroxyl group-containing unsaturated single amounts selected from the group consisting of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate from the viewpoint of further improving water resistance. A unit derived from the body is preferable, and a unit derived from one or more hydroxyl group-containing unsaturated monomers selected from the group consisting of hydrochiethyl (meth) acrylate and hydroxypropyl (meth) acrylate is more preferable.
The hydroxyl group-containing unsaturated monomer that is the raw material of the hydroxyl group-containing unsaturated monomer unit (A) may be hereinafter referred to as “raw material component (a)”.
水酸基含有不飽和単量体単位（Ａ）の含有量は、単量体単位の総量１００質量部に対して、１０質量部以上３５質量部以下であることが好ましい。含有量が１０質量部以上であることにより、水酸基含有不飽和単量体単位（Ａ）のホモポリマーが重合初期に優先的に生成し、得られるラテックスの乾燥皮膜に高い接触角を与える。含有量が３５質量部以下であることにより、ラテックス粘度が低くなることに加え、架橋剤との反応速度が緩やかになる。同様の観点から、含有量は、１０質量部以上３０質量部以下であることが好ましく、１０質量部以上２５質量部以下であることがより好ましい。 The content of the hydroxyl group-containing unsaturated monomer unit (A) is preferably 10 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the total amount of the monomer units. When the content is 10 parts by mass or more, the homopolymer of the hydroxyl group-containing unsaturated monomer unit (A) is preferentially produced at the initial stage of polymerization, and gives a high contact angle to the obtained dry film of latex. When the content is 35 parts by mass or less, the latex viscosity is lowered and the reaction rate with the cross-linking agent is slowed down. From the same viewpoint, the content is preferably 10 parts by mass or more and 30 parts by mass or less, and more preferably 10 parts by mass or more and 25 parts by mass or less.
水酸基含有不飽和単量体単位の含有量は、原料として用いられる水酸基含有不飽和単量体の仕込み量に基づいて算出することができる。但し、重合過程で未反応の単量体が残存することもあるので、この場合は、仕込み量全体から残存した単量体全体を差し引いた値と、水酸基含有不飽和単量体の仕込み量から残存した水酸基含有不飽和単量体を差し引いた値とを算出し、前者の値を１００質量部としたときの後者の値を換算することにより算出することができる。以下、各単量体単位の含有量についても同様の方法により算出できる。 The content of the hydroxyl group-containing unsaturated monomer unit can be calculated based on the amount of the hydroxyl group-containing unsaturated monomer used as a raw material. However, unreacted monomers may remain in the polymerization process. In this case, the value obtained by subtracting the entire remaining monomer from the total charge amount and the charge amount of the hydroxyl group-containing unsaturated monomer are used. It can be calculated by subtracting the remaining hydroxyl group-containing unsaturated monomer and converting the latter value when the former value is 100 parts by mass. Hereinafter, the content of each monomer unit can also be calculated by the same method.
＜脂肪族共役ジエン系単量体単位（Ｂ）＞
本実施形態の共重合体は、耐水性を向上させる観点から、脂肪族共役ジエン系単量体単位（Ｂ）を有することが好ましい。
脂肪族共役ジエン系単量体単位（Ｂ）としては、特に限定されないが、例えば、１，３−ブタジエン、２，３−ジメチル−１，３−ブタジエン、２−エチル−１，３−ブタジエン、２−メチル−１，３−ブタジエン（イソプレン）、２−クロロ−１，３−ブタジエン（クロロプレン）、１，３−ペンタジエン、及びシクロペンタジエンからなる群より選ばれる１種以上の脂肪族共役ジエン系単量体に由来する単位が挙げられる。これらの中でも、入手容易性の観点から、１，３−ブタジエンに由来する単位が好ましい。
なお、脂肪族共役ジエン系単量体単位（Ｂ）の原料となる脂肪族共役ジエン系単量体を以下、「原料成分（ｂ）」と記載することがある。
<Aliphatic conjugated diene-based monomer unit (B)>
The copolymer of the present embodiment preferably has an aliphatic conjugated diene-based monomer unit (B) from the viewpoint of improving water resistance.
The aliphatic conjugated diene-based monomer unit (B) is not particularly limited, and for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, One or more aliphatic conjugated diene systems selected from the group consisting of 2-methyl-1,3-butadiene (isoprene), 2-chloro-1,3-butadiene (chloroprene), 1,3-pentadiene, and cyclopentadiene. Examples include units derived from monomers. Among these, units derived from 1,3-butadiene are preferable from the viewpoint of availability.
The aliphatic conjugated diene-based monomer used as a raw material for the aliphatic conjugated diene-based monomer unit (B) may be hereinafter referred to as “raw material component (b)”.
脂肪族共役ジエン系単量体単位（Ｂ）の含有量は、単量体単位の総量１００質量部に対して、１０質量部以上６５質量部以下であることが好ましい。含有量が１０質量部以上であることにより、良好な成膜性が得られる。含有量が６５質量部以下であることにより、ラテックスを重合する際の機械的安定性を確保できる。同様の観点から、含有量は、２０質量部以上６０質量部以下であることが好ましく、４０質量部以上５５質量部以下であることがより好ましい。 The content of the aliphatic conjugated diene-based monomer unit (B) is preferably 10 parts by mass or more and 65 parts by mass or less with respect to 100 parts by mass of the total amount of the monomer units. When the content is 10 parts by mass or more, good film forming property can be obtained. When the content is 65 parts by mass or less, mechanical stability when polymerizing latex can be ensured. From the same viewpoint, the content is preferably 20 parts by mass or more and 60 parts by mass or less, and more preferably 40 parts by mass or more and 55 parts by mass or less.
＜重合性不飽和単量体単位（Ｃ）＞
本実施形態の重合性不飽和単量体単位（Ｃ）は、水酸基含有不飽和単量体単位（Ａ）及び脂肪族共役ジエン系単量体単位（Ｂ）とは異なる単量体単位である。また、重合性不飽和単量体単位（Ｃ）は、水酸基含有不飽和単量体単位（Ａ）及び脂肪族共役ジエン系単量体単位（Ｂ）の、少なくとも一方と共重合可能な化合物に由来する単位であればよい。
なお、重合性不飽和単量体単位（Ｃ）の原料となる重合性不飽和単量体を以下、「原料成分（ｃ）」と記載することがある。
重合性不飽和単量体単位（Ｃ）としては、例えば、酸性官能基含有不飽和単量体単位（Ｃ１）、不飽和カルボン酸アルキルエステル単量体単位（Ｃ２）、芳香族ビニル単量体単位（Ｃ３）、シアン化ビニル単量体単位（Ｃ４）、無水マレイン酸単量体、（メタ）アクリルアミド単量体、ビニルエステル単量体、ビニルエーテル単量体、ハロゲン化ビニル単量体、アミノ基含有塩基性単量体、ビニルピリジン単量体、オレフィン単量体、ケイ素含有α，β−不飽和性単量体、及びアリル単量体からなる群より選ばれる１種以上の単量体に由来する単位が挙げられる。
<Polymerizable unsaturated monomer unit (C)>
The polymerizable unsaturated monomer unit (C) of the present embodiment is a monomer unit different from the hydroxyl group-containing unsaturated monomer unit (A) and the aliphatic conjugated diene-based monomer unit (B). .. The polymerizable unsaturated monomer unit (C) is a compound copolymerizable with at least one of the hydroxyl group-containing unsaturated monomer unit (A) and the aliphatic conjugated diene-based monomer unit (B). It may be a unit of origin.
The polymerizable unsaturated monomer that is the raw material of the polymerizable unsaturated monomer unit (C) may be hereinafter referred to as “raw material component (c)”.
Examples of the polymerizable unsaturated monomer unit (C) include an acidic functional group-containing unsaturated monomer unit (C1), an unsaturated carboxylic acid alkyl ester monomer unit (C2), and an aromatic vinyl monomer. Unit (C3), vinyl cyanide monomer unit (C4), maleic anhydride monomer, (meth) acrylamide monomer, vinyl ester monomer, vinyl ether monomer, vinyl halide monomer, amino One or more monomers selected from the group consisting of group-containing basic monomers, vinylpyridine monomers, olefin monomers, silicon-containing α, β-unsaturated monomers, and allyl monomers. Units derived from.
中でも、重合性不飽和単量体単位（Ｃ）は、酸性官能基含有不飽和単量体単位（Ｃ１）、不飽和カルボン酸アルキルエステル単量体単位（Ｃ２）、芳香族ビニル単量体単位（Ｃ３）、及びシアン化ビニル単量体単位（Ｃ４）からなる群より選ばれる１種以上であることが好ましい。 Among them, the polymerizable unsaturated monomer unit (C) is an acidic functional group-containing unsaturated monomer unit (C1), an unsaturated carboxylic acid alkyl ester monomer unit (C2), and an aromatic vinyl monomer unit. It is preferably one or more selected from the group consisting of (C3) and the vinyl cyanide monomer unit (C4).
重合性不飽和単量体単位（Ｃ）の含有量は、例えば、単量体単位の総量１００質量部に対して、０質量部以上７５質量部以下である。 The content of the polymerizable unsaturated monomer unit (C) is, for example, 0 parts by mass or more and 75 parts by mass or less with respect to 100 parts by mass of the total amount of the monomer units.
＜酸性官能基含有不飽和単量体単位（Ｃ１）＞
本実施形態の共重合体は、重合初期の分散安定性の観点から、酸性官能基含有不飽和単量体単位（Ｃ１）を有することが好ましい。酸性官能基含有不飽和単量体単位（Ｃ１）としては、特に限定されないが、例えば、一塩基酸単量体、及び二塩基酸単量体からなる群より選ばれる１種以上の単量体に由来する単位が挙げられる。
<Saturated monomer unit containing acidic functional group (C1)>
The copolymer of the present embodiment preferably has an acidic functional group-containing unsaturated monomer unit (C1) from the viewpoint of dispersion stability at the initial stage of polymerization. The acidic functional group-containing unsaturated monomer unit (C1) is not particularly limited, but is, for example, one or more monomers selected from the group consisting of monobasic acid monomer and dibasic acid monomer. Units derived from.
一塩基酸単量体単位としては、特に限定されないが、例えば、（メタ）アクリル酸、クロトン酸、ビニル安息香酸、桂皮酸、スチレンスルホン酸、メタアリルスルホン酸、アリルスルホン酸、ビニルスルホン酸、及びこれらの塩（例えば、ナトリウム塩、カリウム塩、及びアンモニウム塩）からなる群より選ばれる１種以上の一塩基酸単量体に由来する単位が挙げられる。 The monobasic acid monomer unit is not particularly limited, but for example, (meth) acrylic acid, crotonic acid, vinylbenzoic acid, cinnamic acid, styrenesulfonic acid, methallylsulfonic acid, allylsulfonic acid, vinylsulfonic acid, And a unit derived from one or more monobasic acid monomers selected from the group consisting of these salts (eg, sodium salt, potassium salt, and ammonium salt).
二塩基酸単量体単位としては、特に限定されないが、例えば、イタコン酸、フマル酸、マレイン酸、シトラコン酸、ムコン酸、及びこれらの塩（例えば、ナトリウム塩、カリウム塩、及びアンモニウム塩）からなる群より選ばれる１種以上の二塩基酸単量体に由来する単位が挙げられる。 The dibasic acid monomer unit is not particularly limited, but is, for example, from itaconic acid, fumaric acid, maleic acid, citraconic acid, muconic acid, and salts thereof (for example, sodium salt, potassium salt, and ammonium salt). Examples thereof include units derived from one or more kinds of dibasic acid monomers selected from the above group.
酸性官能基含有不飽和単量体単位（Ｃ１）の含有量は、単量体単位の総量１００質量部に対して、０．０１質量部以上０．１質量部以下であることが好ましい。含有量が０．０１質量部以上であることにより、重合初期の分散安定性が向上する。含有量が０．１質量部以下であることにより、ラテックス粘度が低くなることに加え、架橋剤との反応速度が緩やかになる。 The content of the acidic functional group-containing unsaturated monomer unit (C1) is preferably 0.01 parts by mass or more and 0.1 parts by mass or less with respect to 100 parts by mass of the total amount of the monomer units. When the content is 0.01 parts by mass or more, the dispersion stability at the initial stage of polymerization is improved. When the content is 0.1 part by mass or less, the latex viscosity is lowered and the reaction rate with the cross-linking agent is slowed down.
＜不飽和カルボン酸アルキルエステル単量体単位（Ｃ２）＞
本実施形態の共重合体は、塗膜の物性（例えば、ガラス転移温度（Ｔｇ）及び溶解性パラメーター（ｓｐ値））を適宜調整するために、不飽和カルボン酸アルキルエステル単量体単位（Ｃ２）を有してもよい。不飽和カルボン酸アルキルエステル単量体単位（Ｃ２）としては、特に限定されないが、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｎ−アミル（メタ）アクリレート、イソアミルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、２−エチル−ヘキシル（メタ）アクリレート、グリシジル（メタ）アクリレート、グリコールジ（メタ）アクリレート、１，３−ブチレングリコールジ（メタ）アクリレート、１，４−ブチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、１，５−ペンタンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ジグリコールジ（メタ）アクリレート、トリグリコールジ（メタ）アクリレート、テトラグリコールジ（メタ）アクリレート、ポリグリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、アリル（メタ）アクリレート、ビス（４−アクリロキシポリエトキシフェニル）プロパン、メトキシポリエチリングリコール（メタ）アクリレート、β−（メタ）アクリロイルオキシエチルハイドロジェンフタレート、β−（メタ）アクリロイルオキシエチルハイドロジェンサクシネート、ステアリル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシポリグリコール（メタ）アクリレート、２，２−ビス［４−（（メタ）アクリロキシエトキシ）フェニル］プロパン、２，２−ビス［４−（（メタ）アクリロキシ・ジエトキシ）フェニル］プロパン、２，２−ビス［４−（（メタ）アクリロキシ・ポリエトキシ）フェニル］プロパン、及びイソボルニル（メタ）アクリレートからなる群より選ばれる１種以上の単量体に由来する単位が挙げられる。
<Unsaturated carboxylic acid alkyl ester monomer unit (C2)>
The copolymer of the present embodiment has an unsaturated carboxylic acid alkyl ester monomer unit (C2) in order to appropriately adjust the physical properties of the coating film (for example, glass transition temperature (Tg) and solubility parameter (sp value)). ) May have. The unsaturated carboxylic acid alkyl ester monomer unit (C2) is not particularly limited, and is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t. -Butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, isoamylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) Acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-ethyl-hexyl (meth) acrylate, glycidyl (meth) acrylate, glycol di (meth) acrylate, 1 , 3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, 1,6-hexanediol di (meth) acrylate, diglycol di (meth) acrylate, triglycol di (meth) acrylate, tetraglycol di (meth) acrylate, polyglycol di (meth) acrylate, polypropylene glycol di ( Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Trimethylol Propane Tri (Meta) Acrylate, Tetramethylol Methantetra (Meta) Acrylate, Allyl (Meta) Acrylate, Bis (4-Acryloxipolyethoxyphenyl) Propane, methoxypolyethi Phosphoryl glycol (meth) acrylate, β- (meth) acryloyloxyethyl hydrogen phthalate, β- (meth) acryloyloxyethyl hydrogen succinate, stearyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyglycol (meth) ) Acrylate, 2,2-bis [4-((meth) acryloxyethoxy) phenyl] propane, 2,2-bis [4-((meth) acryloxydiethoxy) phenyl] propane, 2,2-bis [4 -((Meta) acryloxy-polyethoxy) phenyl] Propane, and one or more monomers selected from the group consisting of isobornyl (meth) acrylate. The unit to come is mentioned.
不飽和カルボン酸アルキルエステル単量体単位（Ｃ２）の含有量は、塗膜の使用目的により適宜調整してもよく、例えば、単量体単位の総量１００質量部に対して、０を超えて、７５質量部以下であってもよい。 The content of the unsaturated carboxylic acid alkyl ester monomer unit (C2) may be appropriately adjusted depending on the purpose of use of the coating film, and for example, exceeds 0 with respect to 100 parts by mass of the total amount of the monomer unit. , 75 parts by mass or less.
＜芳香族ビニル単量体単位（Ｃ３）＞
本実施形態の共重合体は、塗膜の物性（例えば、ガラス転移温度（Ｔｇ）及び溶解性パラメーター（ｓｐ値））を適宜調整するために、芳香族ビニル単量体単位（Ｃ３）を有してもよい。芳香族ビニル単量体単位（Ｃ３）としては、特に限定されないが、例えば、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、エチルスチレン、ビニルトルエン、ビニルキシレン、ブロモスチレン、ビニルベンジルクロリド、ｐ−ｔ−ブチルスチレン、クロロスチレン、アルキルスチレン、ジビニルベンゼン、及びトリビニルベンゼンからなる群より選ばれる１種以上の単量体に由来する単量体単位が挙げられる。
<Aromatic vinyl monomer unit (C3)>
The copolymer of the present embodiment has an aromatic vinyl monomer unit (C3) in order to appropriately adjust the physical properties of the coating film (for example, the glass transition temperature (Tg) and the solubility parameter (sp value)). You may. The aromatic vinyl monomer unit (C3) is not particularly limited, but for example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ethylstyrene, vinyltoluene, vinylxylene. , Bromostyrene, vinylbenzyl chloride, pt-butylstyrene, chlorostyrene, alkylstyrene, divinylbenzene, and trivinylbenzene, and the monomer units derived from one or more monomers selected from the group. Be done.
芳香族ビニル単量体単位（Ｃ３）の含有量は、塗膜の使用目的により適宜調整してもよく、例えば、単量体単位の総量１００質量部に対して、３質量部以上５０質量部以下であってもよい。 The content of the aromatic vinyl monomer unit (C3) may be appropriately adjusted depending on the purpose of use of the coating film. For example, 3 parts by mass or more and 50 parts by mass with respect to 100 parts by mass of the total amount of the monomer units. It may be as follows.
＜シアン化ビニル単量体単位（Ｃ４）＞
本実施形態の共重合体は、塗膜の物性（例えば、ガラス転移温度（Ｔｇ）及び溶解性パラメーター（ｓｐ値））を適宜調整するために、シアン化ビニル単量体単位（Ｃ４）を有してもよい。シアン化ビニル単量体単位（Ｃ４）としては、特に限定されないが、例えば、（メタ）アクリロニトリルに由来する単量体単位が挙げられる。
<Vinyl cyanide monomer unit (C4)>
The copolymer of the present embodiment has a vinyl cyanide monomer unit (C4) in order to appropriately adjust the physical properties of the coating film (for example, the glass transition temperature (Tg) and the solubility parameter (sp value)). You may. The vinyl cyanide monomer unit (C4) is not particularly limited, and examples thereof include a monomer unit derived from (meth) acrylonitrile.
シアン化ビニル単量体単位（Ｃ４）の含有量は、塗膜の使用目的により適宜調整してもよく、例えば、単量体単位の総量１００質量部に対して、０を超えて１０質量部以下であってもよい。 The content of the vinyl cyanide monomer unit (C4) may be appropriately adjusted depending on the purpose of use of the coating film. For example, the content of the vinyl cyanide monomer unit (C4) exceeds 0 to 10 parts by mass with respect to 100 parts by mass of the total amount of the monomer units. It may be as follows.
（メタ）アクリルアミド単量体単位としては、特に限定されないが、例えば、（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、及びＮ−アルコキシ（メタ）アクリルアミドからなる群より選ばれる１種以上の単量体に由来する単量体単位が挙げられる。 The (meth) acrylamide monomer unit is not particularly limited, and is, for example, one or more simple units selected from the group consisting of (meth) acrylamide, N-methylol (meth) acrylamide, and N-alkoxy (meth) acrylamide. Examples include monomeric units derived from alkoxy groups.
ビニルエステル単量体単位としては、特に限定されないが、例えば、酢酸ビニル、ビニルブチレート、ビニルステアレート、ビニルラウレート、ビニルミリステート、ビニルプロピオネート、及びバーサティク酸ビニルからなる群より選ばれる１種以上の単量体に由来する単量体単位が挙げられる。 The vinyl ester monomer unit is not particularly limited, but is selected from the group consisting of, for example, vinyl acetate, vinyl butyrate, vinyl stearate, vinyl laurate, vinyl millistate, vinyl propionate, and vinyl versaticate. Examples thereof include a monomer unit derived from one or more kinds of monomers.
ビニルエーテル単量体単位としては、特に限定されないが、例えば、メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、アミルビニルエーテル、及びヘキシルビニルエーテルからなる群より選ばれる１種以上の単量体に由来する単量体単位が挙げられる。 The vinyl ether monomer unit is not particularly limited, but is simply derived from one or more monomers selected from the group consisting of, for example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether, and hexyl vinyl ether. The unit of measure can be mentioned.
ハロゲン化ビニル単量体単位としては、特に限定されないが、例えば、塩化ビニル、臭化ビニル、フッ化ビニル、塩化ビニリデン、及びフッ化ビニリデンからなる群より選ばれる１種以上の単量体に由来する単量体単位が挙げられる。 The vinyl halide monomer unit is not particularly limited, and is derived from, for example, one or more monomers selected from the group consisting of vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, and vinylidene chloride. The monomer unit to be used can be mentioned.
アミノ基含有塩基性単量体単位としては、特に限定されないが、例えば、アミノエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、及びジエチルアミノエチル（メタ）アクリレートからなる群より選ばれる１種以上の単量体に由来する単量体単位が挙げられる。 The amino group-containing basic monomer unit is not particularly limited, and is, for example, one or more selected from the group consisting of aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate. Examples thereof include a monomer unit derived from the monomer of.
オレフィン単量体単位としては、特に限定されないが、例えば、エチレン、及びプロピレンからなる群より選ばれる１種以上の単量体に由来する単量体単位が挙げられる。 The olefin monomer unit is not particularly limited, and examples thereof include a monomer unit derived from one or more kinds of monomers selected from the group consisting of ethylene and propylene.
ケイ素含有α，β−不飽和性単量体単位としては、特に限定されないが、例えば、ビニルトリクロルシラン、及びビニルトリエトキシシランからなる群より選ばれる１種以上の単量体に由来する単量体単位が挙げられる。 The silicon-containing α, β-unsaturated monomer unit is not particularly limited, but is, for example, a single amount derived from one or more monomers selected from the group consisting of vinyltrichlorosilane and vinyltriethoxysilane. The body unit can be mentioned.
アリル単量体単位としては、特に限定されないが、例えば、アリルエステル、及びジアリルフタレートからなる群より選ばれる１種以上の単量体に由来する単量体単位が挙げられる。 The allyl monomer unit is not particularly limited, and examples thereof include a monomer unit derived from one or more kinds of monomers selected from the group consisting of allyl ester and diallyl phthalate.
重合性不飽和単量体単位（Ｃ）の重合性不飽和基の数は、２つ以上であってもよい。重合性不飽和基の数が３である単量体に由来する単位としては、例えば、トリアリルイソシアヌレートに由来する単位が挙げられる。 The number of polymerizable unsaturated groups in the polymerizable unsaturated monomer unit (C) may be two or more. Examples of the unit derived from the monomer having 3 polymerizable unsaturated groups include a unit derived from triallyl isocyanurate.
＜イソシアネート系硬化剤＞
本実施形態の水系組成物は、イソシアネート系硬化剤（架橋剤）を更に含んでいてもよい。イソシアネート系硬化剤は、２個以上のイソシアネート基を有することが好ましい。イソシアネート系硬化剤としては、例えば、ジフェニルメタン−４，４’−ジイソシアネート、トリレンジイソシアネート及びその水素化物、トリフェニルメタントリイソシアネート、トリメチロールプロパン−トリレンジイソシアネートアダクト、ジフェニルメタンジイソシアネート［ＭＤＩ（メチレンジ（４−フェニルイソシアネート）、クルードＭＤＩを含む）］及びその水素化物、ヘキサメチレンジイソシアネート、キシレンジイソシアネート、イソホロンジイソシアネート、４、４’−ジシクロヘキシルメタンジイソシアネート等が挙げられる。これらに高沸点溶剤等を配合したものも使用できる。また、ポリエステル等のポリオールに上記イソシアネート系硬化剤を過剰に混合したもの、ポリオールと過剰のポリイソシアネートとで予めポリマー化したＯＨ基末端プレポリマー、過剰のポリオールで予めポリマー化したＯＨ基末端プレポリマーにポリイソシアネート系硬化剤を過剰に加えたもの、ノニオン界面活性剤を含有するポリイソシアネート等も使用できる。
<Isocyanate-based curing agent>
The aqueous composition of the present embodiment may further contain an isocyanate-based curing agent (crosslinking agent). The isocyanate-based curing agent preferably has two or more isocyanate groups. Examples of the isocyanate-based curing agent include diphenylmethane-4,4'-diisocyanate, tolylene diisocyanate and its hydride, triphenylmethane triisocyanate, trimethylolpropan-tolylene diisocyanate adduct, and diphenylmethane diisocyanate [MDI (methylene di (4-4-) Phenylisocyanate), including crude MDI)] and hydrides thereof, hexamethylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, 4, 4'-dicyclohexylmethane diisocyanate and the like. Those containing a high boiling point solvent or the like can also be used. In addition, a polyol such as polyester mixed with the above isocyanate-based curing agent in excess, an OH group-terminated prepolymer prepolymerized with a polyol and an excess polyisocyanate, and an OH group-terminated prepolymer prepolymerized with an excess polyol. A polymer containing an excessive amount of a polyisocyanate-based curing agent, a polymer containing a nonionic surfactant, or the like can also be used.
水系組成物に含まれる硬化剤の含有量は、水系組成物を基準として、好ましくは１０〜４０質量％であり、より好ましくは２０〜３０質量％である。硬化剤の含有量が１０質量％以上であることにより、評価に適した反応速度が得られる。イソシアネート系硬化剤の含有量が４０質量％以下であることにより、架橋剤との反応速度を緩やかにできる。 The content of the curing agent contained in the water-based composition is preferably 10 to 40% by mass, more preferably 20 to 30% by mass, based on the water-based composition. When the content of the curing agent is 10% by mass or more, a reaction rate suitable for evaluation can be obtained. When the content of the isocyanate-based curing agent is 40% by mass or less, the reaction rate with the cross-linking agent can be slowed down.
本実施形態の水系組成物は、例えば、前記共重合体が水中で分散した分散液の形態を有している。水系組成物の固形分濃度は、特に限定されないが、例えば、１０〜６０質量％程度であってもよい。 The aqueous composition of the present embodiment has, for example, the form of a dispersion in which the copolymer is dispersed in water. The solid content concentration of the aqueous composition is not particularly limited, but may be, for example, about 10 to 60% by mass.
本実施形態の水系組成物のｐＨは、特に限定されないが、安定性と取り扱い性の観点から、ｐＨ３〜１０であることが好ましい。 The pH of the aqueous composition of the present embodiment is not particularly limited, but is preferably pH 3 to 10 from the viewpoint of stability and handleability.
＜粘度＞
本実施形態の水系組成物は、イソシアネート系硬化剤と混合した後に所定の粘度を有する。具体的には、水系組成物と炭酸カルシウムとポリビニルアルコールとの混合物に、ジフェニルメタン−４，４’−ジイソシアネートを添加し３０分放置した後の粘度（以下「３０分後粘度」という。）が、添加直後の粘度（以下「直後粘度」という。）の５．８倍以下である。直後粘度に対する３０分後粘度の比率（以下「粘度上昇率」という。）が低いほど、前記混合物に含まれる共重合体とイソシアネート系硬化剤との反応（架橋）速度が遅いことを意味する。反応速度が遅いほど、架橋反応に関与しない共重合体の単量体単位が共重合体粒子の外側に移動することによって、水接触角が大きくなる傾向にあり、これにより耐水性が向上する。
一般にOH基を多量持つポリマーは接触角が低く耐水性が悪い。そして耐水性を向上させる手段として、本実施形態においては硬化剤配合後の粘度上昇率を規定する。本実施形態における共重合体にはOH基を持つモノマー由来の部分と持たないモノマー由来の部分が含まれるが、OH基を持つモノマー由来の部分が選択的に粒子内部に取り込まれた構造となっているので、架橋反応が進行しづらく粘度上昇率が低い。
本実施形態においては粘度上昇率が一定値以下である水系組成物を採用することにより、親水性に悪影響がある部分が粒子内部に取り込まれていることで高い接触角が実現されるものと考えられる。
<Viscosity>
The aqueous composition of the present embodiment has a predetermined viscosity after being mixed with an isocyanate-based curing agent. Specifically, the viscosity after adding diphenylmethane-4,4'-diisocyanate to a mixture of an aqueous composition, calcium carbonate and polyvinyl alcohol and leaving it for 30 minutes (hereinafter referred to as "viscosity after 30 minutes") is determined. It is 5.8 times or less of the viscosity immediately after addition (hereinafter referred to as "immediate viscosity"). The lower the ratio of the viscosity after 30 minutes to the viscosity immediately after (hereinafter referred to as "viscosity increase rate"), the slower the reaction (crosslinking) rate between the copolymer contained in the mixture and the isocyanate-based curing agent. The slower the reaction rate, the larger the water contact angle tends to be due to the movement of the monomer unit of the copolymer that is not involved in the crosslinking reaction to the outside of the copolymer particles, which improves the water resistance.
Generally, a polymer having a large amount of OH groups has a low contact angle and poor water resistance. Then, as a means for improving the water resistance, in the present embodiment, the viscosity increase rate after blending the curing agent is defined. The copolymer in the present embodiment contains a monomer-derived portion having an OH group and a monomer-derived portion not having an OH group, but the structure is such that the monomer-derived portion having an OH group is selectively incorporated into the particles. Therefore, the cross-linking reaction is difficult to proceed and the rate of increase in viscosity is low.
In this embodiment, it is considered that by adopting an aqueous composition having a viscosity increase rate of a certain value or less, a high contact angle can be realized by incorporating a portion having an adverse effect on hydrophilicity inside the particles. Be done.
粘度上昇率は、５．８倍以下、好ましくは５．０倍以下であり、より好ましくは４．０倍以下であり、更に好ましくは３．０倍以下であり、特に好ましくは２．０倍以下である。粘度上昇率は低いほど好ましいため、粘度上昇率の下限は、特に限定されないが、例えば、１．２倍、１．４倍、１．６倍等としてもよい。 The viscosity increase rate is 5.8 times or less, preferably 5.0 times or less, more preferably 4.0 times or less, still more preferably 3.0 times or less, and particularly preferably 2.0 times or less. It is as follows. The lower the viscosity increase rate is, the more preferable it is. Therefore, the lower limit of the viscosity increase rate is not particularly limited, but may be, for example, 1.2 times, 1.4 times, 1.6 times, or the like.
直後粘度としては、例えば、１．０Ｐａ・ｓ〜１５．０Ｐａ・ｓ、２．０Ｐａ・ｓ〜１０．０Ｐａ・ｓ、３．０Ｐａ・ｓ〜７．０Ｐａ・ｓ等が挙げられ、より具体的には３．８Ｐａ・ｓ〜３．９Ｐａ・ｓ、４．４Ｐａ・ｓ〜４．５Ｐａ・ｓ、５．８Ｐａ・ｓ〜５．９Ｐａ・ｓ等が挙げられる。
３０分後粘度としては、例えば、６．０Ｐａ・ｓ〜５０．０Ｐａ・ｓ、８．０Ｐａ・ｓ〜４０．０Ｐａ・ｓ、１０．０Ｐａ・ｓ〜３０．０Ｐａ・ｓ等が挙げられ、より具体的には１６．６Ｐａ・ｓ〜１６．７Ｐａ・ｓ、２５．８Ｐａ・ｓ〜２５．９Ｐａ・ｓ、１１．６Ｐａ・ｓ〜１１．７Ｐａ・ｓ等が挙げられる。
Immediately after the viscosity, for example, 1.0 Pa · s to 15.0 Pa · s, 2.0 Pa · s to 10.0 Pa · s, 3.0 Pa · s to 7.0 Pa · s and the like can be mentioned, and more concretely. Examples include 3.8 Pa · s to 3.9 Pa · s, 4.4 Pa · s to 4.5 Pa · s, 5.8 Pa · s to 5.9 Pa · s, and the like.
Examples of the viscosity after 30 minutes include 6.0 Pa · s to 50.0 Pa · s, 8.0 Pa · s to 40.0 Pa · s, 10.0 Pa · s to 30.0 Pa · s, and the like. Specific examples thereof include 16.6 Pa · s to 16.7 Pa · s, 25.8 Pa · s to 25.9 Pa · s, 11.6 Pa · s to 11.7 Pa · s, and the like.
粘度上昇率は、ジフェニルメタン−４，４’−ジイソシアネートを介した共重合体の架橋の度合いによって変化する。そのため、ジフェニルメタン−４，４’−ジイソシアネートと反応性の官能基を含む単量体単位の含有量を調節することによって、粘度上昇率を調節することができる。当業者であれば、共重合体の組成を適宜変更して、適切な粘度上昇率を達成することができる。 The rate of increase in viscosity varies depending on the degree of cross-linking of the copolymer via diphenylmethane-4,4'-diisocyanate. Therefore, the rate of increase in viscosity can be adjusted by adjusting the content of the monomer unit containing a functional group reactive with diphenylmethane-4,4'-diisocyanate. Those skilled in the art can appropriately change the composition of the copolymer to achieve an appropriate viscosity increase rate.
（接触角）
本実施形態の水系組成物は、大きい水接触角を有する塗膜を形成することが好ましい。水接触角が大きい塗膜は耐水性に優れる。塗膜の水接触角は、好ましくは６５°以上であり、より好ましくは７０°以上であり、更に好ましくは８０°以上である。塗膜の水接触角の上限は、特に限定されないが、例えば、１３０°、１１０°、９０°等としてもよい。塗膜の水接触角は、実施例に記載の方法で測定する。
(Contact angle)
The water-based composition of the present embodiment preferably forms a coating film having a large water contact angle. A coating film having a large water contact angle has excellent water resistance. The water contact angle of the coating film is preferably 65 ° or more, more preferably 70 ° or more, and further preferably 80 ° or more. The upper limit of the water contact angle of the coating film is not particularly limited, but may be, for example, 130 °, 110 °, 90 °, or the like. The water contact angle of the coating film is measured by the method described in Examples.
（平均粒子径）
本実施形態の共重合体の平均粒子径としては、好ましくは１００ｎｍ〜６００ｎｍ、より好ましくは１５０ｎｍ〜５００ｎｍ、更に好ましくは１５０ｎｍ〜２５０ｎｍ、特に好ましくは１５０ｎｍ〜２２０ｎｍである。平均粒子径が１００ｎｍ以上であることにより、架橋剤との反応速度を緩やかにできる。平均粒子径が６００ｎｍ以下であることにより、ラテックス粒子の沈降を防ぐことができる。
共重合体の平均粒子径は、シードラテックス、界面活性剤を所望の割合で使用することにより調整できる。通常、その使用量を大きくすることにより、共重合体の平均粒子径は小さくなる傾向にある。
(Average particle size)
The average particle size of the copolymer of the present embodiment is preferably 100 nm to 600 nm, more preferably 150 nm to 500 nm, still more preferably 150 nm to 250 nm, and particularly preferably 150 nm to 220 nm. When the average particle size is 100 nm or more, the reaction rate with the cross-linking agent can be slowed down. When the average particle size is 600 nm or less, sedimentation of latex particles can be prevented.
The average particle size of the copolymer can be adjusted by using a seed latex and a surfactant in a desired ratio. Usually, the average particle size of the copolymer tends to decrease as the amount used increases.
（ゲル分率）
本実施形態の共重合体は、好ましくは７５〜９５％、より好ましくは８０〜９０％のゲル分率を有する。ゲル分率が７５％以上であることにより、架橋剤との反応速度を緩やかにできる。ゲル分率が９５％以下であることにより、架橋反応が効率的に進行する。
(Gel fraction)
The copolymer of the present embodiment preferably has a gel fraction of 75 to 95%, more preferably 80 to 90%. When the gel fraction is 75% or more, the reaction rate with the cross-linking agent can be slowed down. When the gel fraction is 95% or less, the cross-linking reaction proceeds efficiently.
（ガラス転移温度）
本実施形態の共重合体ラテックスのガラス転移温度Ｔｇは、−６０℃以上４０℃以下であることが好ましく、−５０℃以上１０℃以下であることがより好ましい。ガラス転移温度Ｔｇが−６０℃以上であることにより、ラテックスを重合する際の機械的安定性を確保できる。ガラス転移温度Ｔｇが４０℃以下であることにより、良好な製膜性が得られる。
(Glass-transition temperature)
The glass transition temperature Tg of the copolymer latex of the present embodiment is preferably −60 ° C. or higher and 40 ° C. or lower, and more preferably −50 ° C. or higher and 10 ° C. or lower. When the glass transition temperature Tg is −60 ° C. or higher, mechanical stability when polymerizing latex can be ensured. When the glass transition temperature Tg is 40 ° C. or lower, good film forming property can be obtained.
［本実施形態の水系組成物の製造方法］
本実施形態の水系組成物の製造方法は、水酸基含有不飽和単量体、及び脂肪族共役ジエン系単量体を重合する重合工程を含み、前記重合工程を実施する前に、前記製造方法で使用される水酸基含有不飽和単量体の全量が前記脂肪族共役ジエン系単量体と混合される。全量の水酸基含有不飽和単量体を重合工程の実施前に加えることにより、水酸基含有不飽和単量体がラテックス粒子の内側に存在できるようになり、粘度上昇率を低下させることができる。
[Method for producing aqueous composition of the present embodiment]
The method for producing an aqueous composition of the present embodiment includes a polymerization step of polymerizing a hydroxyl group-containing unsaturated monomer and an aliphatic conjugated diene-based monomer, and the production method is used before the polymerization step is carried out. The total amount of the hydroxyl group-containing unsaturated monomer used is mixed with the aliphatic conjugated diene-based monomer. By adding the total amount of the hydroxyl group-containing unsaturated monomer before the polymerization step, the hydroxyl group-containing unsaturated monomer can be present inside the latex particles, and the viscosity increase rate can be reduced.
本実施形態の水系組成物の製造方法に使用する単量体の詳細は、前記［水系組成物］の項目で記載したとおりである。なお、各単量体の仕込み量は、各単量体に対応する単量体単位の含有量として、前記［水系組成物］の項目において記載した量とすることができる。 The details of the monomer used in the method for producing the aqueous composition of the present embodiment are as described in the item of [Aqueous composition] above. The amount of each monomer charged can be the amount described in the item of [Aqueous composition] as the content of the monomer unit corresponding to each monomer.
単量体を重合する方法としては、特に限定されないが、例えば、公知の乳化重合による方法が挙げられる。より詳細には、重合可能な温度に調整された反応系に、あらかじめ水、界面活性剤、重合開始剤、及びその他添加剤を含む原料（以下「第１原料」ともいう。）を仕込み、次に、この反応系に単量体、連鎖移動剤、及び重合反応抑制剤を含む原料（以下「第２原料」ともいう。）及び、水、ｐＨ調整剤、界面活性剤、及び重合開始剤を含む原料（以下「第３原料」ともいう。）を同時又は逐次的に反応系内に仕込むことにより乳化重合させる方法が挙げられる。この重合工程において、各原料は、回分操作又は連続操作により反応系内に仕込んでもよい。なお、単量体が、二塩基酸単量体を含む場合には、二塩基酸単量体を第１原料に含めてもよい。 The method for polymerizing the monomer is not particularly limited, and examples thereof include a known method by emulsion polymerization. More specifically, a raw material containing water, a surfactant, a polymerization initiator, and other additives (hereinafter, also referred to as “first raw material”) is charged in advance into a reaction system adjusted to a polymerizable temperature, and then In addition, a raw material containing a monomer, a chain transfer agent, and a polymerization reaction inhibitor (hereinafter, also referred to as "second raw material"), water, a pH adjuster, a surfactant, and a polymerization initiator in this reaction system are added. Examples thereof include a method of emulsifying polymerization by simultaneously or sequentially charging the containing raw material (hereinafter, also referred to as “third raw material”) into the reaction system. In this polymerization step, each raw material may be charged into the reaction system by a batch operation or a continuous operation. When the monomer contains a dibasic acid monomer, the dibasic acid monomer may be included in the first raw material.
また、必要に応じて反応系には、シードラテックス、重合開始剤、その他の調整剤を、第２原料を仕込む前にあらかじめ仕込んでおいてもよい。また、単量体、その他の添加剤又は調整剤を反応系へ添加することにより、得られる共重合体粒子の層構造の各物性（例えば、親水性、ガラス転移温度、分子量、架橋密度など）を段階的に変えることができる。なお、本実施形態において、共重合体の層構造の段階数は特に制限されない。 Further, if necessary, the reaction system may be preliminarily charged with a seed latex, a polymerization initiator, and other adjusting agents before the second raw material is charged. In addition, each physical property of the layer structure of the copolymer particles obtained by adding a monomer or other additive or modifier to the reaction system (for example, hydrophilicity, glass transition temperature, molecular weight, crosslink density, etc.) Can be changed step by step. In the present embodiment, the number of stages of the layer structure of the copolymer is not particularly limited.
＜界面活性剤＞
界面活性剤としては、従来公知のアニオン、カチオン、両性及び非イオン性の界面活性剤を用いることができる。これらの中でも、界面活性剤は、脂肪族セッケン、ロジン酸セッケン、アルキルスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩、アルキルスルホコハク酸塩、ポリオキシエチレンアルキル硫酸塩などのアニオン性界面活性剤；ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレンオキシプロピレンブロックコポリマーなどのノニオン性界面活性剤であることが好ましい。これらの界面活性剤は、１種を単独で、又は２種以上を組み合わせて用いることができる。
<Surfactant>
As the surfactant, conventionally known anionic, cationic, amphoteric and nonionic surfactants can be used. Among these, surfactants are anionic surfactants such as aliphatic surfactants, loginate surfactants, alkyl sulfonates, alkyl diphenyl ether disulfonates, alkyl sulfosuccinates, and polyoxyethylene alkyl sulfates; polyoxyethylene. It is preferably a nonionic surfactant such as an alkyl ether, a polyoxyethylene alkyl allyl ether, or a polyoxyethylene oxypropylene block copolymer. These surfactants can be used alone or in combination of two or more.
界面活性剤の仕込み量（使用量）は、単量体の総量１００質量部に対して、好ましくは０．０１質量部〜２．０質量部、より好ましくは０．０１質量部〜１．３質量部、さらに好ましくは０．０１質量部〜０．８質量部であってもよい。 The amount of the surfactant charged (used amount) is preferably 0.01 parts by mass to 2.0 parts by mass, and more preferably 0.01 parts by mass to 1.3 parts with respect to 100 parts by mass of the total amount of the monomer. It may be parts by mass, more preferably 0.01 parts by mass to 0.8 parts by mass.
＜反応性乳化剤＞
分子中にビニル基、アクリロイル基、メタクリロイル基などのラジカル重合性の二重結合を有する反応性乳化剤を用いてもよい。反応性乳化剤は、第１原料〜第３原料のいずれに含まれていてもよい。また、反応性乳化剤を仕込む場合、単量体の仕込み総量に反応性乳化剤の仕込み量も含まれる。
<Reactive emulsifier>
A reactive emulsifier having a radically polymerizable double bond such as a vinyl group, an acryloyl group, or a methacryloyl group in the molecule may be used. The reactive emulsifier may be contained in any of the first to third raw materials. When the reactive emulsifier is charged, the total amount of the monomer charged includes the amount of the reactive emulsifier charged.
＜重合開始剤＞
重合開始剤は、熱又は還元性物質の存在下ラジカル分解して単量体の付加重合を開始させるラジカル重合開始剤であれば特に限定されず、無機系ラジカル重合開始剤及び有機系ラジカル重合開始剤のいずれも使用できる。ラジカル重合開始剤の具体例としては、水溶性又は油溶性のペルオキソ二硫酸塩、過酸化物、アゾビス化合物等、具体的にはペルオキソ二硫酸カリウム、ペルオキソ二硫酸ナトリウム、ペルオキソ二硫酸アンモニウム、過酸化水素、ｔ−ブチルヒドロペルオキシド、過酸化ベンゾイル、２，２−アゾビスブチロニトリル、クメンハイドロパーオキサイド等が挙げられ、また、これら以外にも、ＰＯＬＹＭＥＲ ＨＡＮＤＢＯＯＫ （３ｒｄ ｅｄｉｔｉｏｎ）、Ｊ．Ｂｒａｎｄｒｕｐ及びＥ．Ｈ．Ｉｍｍｅｒｇｕｔ著、Ｊｏｈｎ Ｗｉｌｌｙ＆Ｓｏｎｓ刊（１９８９）のラジカル重合開始剤として記載された化合物も挙げられる。これらの重合開始剤は、１種を単独で、又は２種以上を組み合わせて用いることができる。
<Polymerization initiator>
The polymerization initiator is not particularly limited as long as it is a radical polymerization initiator that radically decomposes in the presence of heat or a reducing substance to initiate addition polymerization of the monomer, and an inorganic radical polymerization initiator and an organic radical polymerization initiator are initiated. Any of the agents can be used. Specific examples of the radical polymerization initiator include water-soluble or oil-soluble peroxodisulfate, peroxide, azobis compound, etc., specifically, potassium peroxodisulfate, sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide. , T-Butylhydroperoxide, benzoyl peroxide, 2,2-azobisbutyronitrile, cumenehydroperoxide and the like, and in addition to these, POLYMER HANDBOOK (3rd edition), J. Mol. Brandrup and E.I. H. Also mentioned are compounds described as radical polymerization initiators by Immunogut, published by John Willy & Sons (1989). These polymerization initiators can be used alone or in combination of two or more.
また、本実施形態において、酸性亜硫酸ナトリウム、アスコルビン酸やその塩、エリソルビン酸やその塩、ロンガリット等の還元剤を重合開始剤に組み合わせて用いる、いわゆるレドックス重合法を採用してもよい。これらの中では、ペルオキソ二硫酸塩が重合開始剤として好適である。この重合開始剤の仕込み量（使用量）は、重合時の安定性の観点から、単量体の総量１００質量部に対して、０．１質量部以上５．０質量部以下であることが好ましく、０．２質量部以上３．０質量部以下であることがより好ましい。 Further, in the present embodiment, a so-called redox polymerization method may be adopted in which a reducing agent such as acidic sodium bisulfite, ascorbic acid or a salt thereof, erythorbic acid or a salt thereof, or longalit is used in combination with a polymerization initiator. Of these, peroxodisulfate is suitable as the polymerization initiator. From the viewpoint of stability during polymerization, the amount of the polymerization initiator charged (used) is 0.1 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the total amount of the monomers. It is preferably 0.2 parts by mass or more and 3.0 parts by mass or less.
＜重合反応抑制剤＞
重合反応抑制剤としては、乳化重合系に添加することにより、ラジカル重合速度を低下させることができる化合物が挙げられ、重合速度遅延剤、重合禁止剤、ラジカル再開始反応性が低い連鎖移動剤、及びラジカル再開始反応性が低い単量体が挙げられる。
<Polymerization reaction inhibitor>
Examples of the polymerization reaction inhibitor include compounds that can reduce the radical polymerization rate by adding to the emulsion polymerization system, such as a polymerization rate retarder, a polymerization inhibitor, and a chain transfer agent having a low radical restart reactivity. And a monomer having a low radical restart reactivity.
重合反応抑制剤は、重合反応速度の調整及び共重合体の物性の調整に用いられる。これらの重合反応抑制剤は、回分操作又は連続操作で反応系に添加してもよい。重合反応抑制剤を用いる場合、塗膜の強度がより向上する傾向にある。重合反応抑制剤はポリマーの立体構造に密接に関与していると思われ、これにより塗膜の物性の調整に効果があるものと推測されるが、この推測により本発明は何ら限定されない。 The polymerization reaction inhibitor is used for adjusting the polymerization reaction rate and adjusting the physical properties of the copolymer. These polymerization reaction inhibitors may be added to the reaction system by batch operation or continuous operation. When a polymerization reaction inhibitor is used, the strength of the coating film tends to be further improved. The polymerization reaction inhibitor is considered to be closely involved in the three-dimensional structure of the polymer, and it is presumed that this is effective in adjusting the physical properties of the coating film, but this speculation does not limit the present invention at all.
重合反応抑制剤としては、特に限定されないが、例えば、ｏ−，ｍ−，又はｐ−ベンゾキノン等のキノン類、ニトロベンゼン、ｏ−，ｍ−，又はｐ−ジニトロベンゼン等のニトロ化合物、ジフェニルアミン等のアミン類、第三ブチルカテコール等のカテコール誘導体、１，１−ジフェニル又はα−メチルスチレン、２，４−ジフェニル−４−メチル−１−ペンテン等の１，１−ジ置換ビニル化合物、２，４−ジフェニル−４−メチル−２−ペンテン、シクロヘキセン等の１，２−ジ置換ビニル化合物等が挙げられる。これら以外にも、「ＰＯＬＹＭＥＲ ＨＡＮＤＢＯＯＫ ３ｒｄ Ｅｄ．（Ｊ．Ｂｒａｎｄｕｐ，Ｅ．Ｈ．Ｉｍｍｅｒｇｕｔ：Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ，１９８９）」、「改訂高分子合成の化学（大津：化学同人、１９７９．）」の重合禁止剤又は重合抑制剤として記載された化合物が挙げられる。これらの重合反応抑制剤は、１種を単独で、又は２種以上を組み合わせて用いてもよい。 The polymerization reaction inhibitor is not particularly limited, but for example, quinones such as o-, m-, or p-benzoquinone, nitro compounds such as nitrobenzene, o-, m-, or p-dinitrobenzene, diphenylamine, and the like. Amines, catechol derivatives such as tertiary butylcatechol, 1,1-disubstituted vinyl compounds such as 1,1-diphenyl or α-methylstyrene, 2,4-diphenyl-4-methyl-1-pentene, 2,4 Examples thereof include 1,2-di-substituted vinyl compounds such as −diphenyl-4-methyl-2-pentene and cyclohexene. In addition to these, the polymerization of "POLYMER HANDBOOK 3rd Ed. (J. Brandup, E.H. Immunogut: John Wiley & Sons, 1989)" and "Revised Polymer Synthesis Chemistry (Otsu: Kagaku-Dojin, 1979.)" Examples include compounds described as bans or polymerization inhibitors. These polymerization reaction inhibitors may be used alone or in combination of two or more.
重合反応抑制剤は、これらの中でも、反応性の観点から、２，４−ジフェニル−４−メチル−１−ペンテン（α−メチルスチレンダイマー）が好ましい。 Among these, the polymerization reaction inhibitor is preferably 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene dimer) from the viewpoint of reactivity.
重合反応抑制剤の仕込み量（使用量）は、単量体の総量１００質量部に対して、重合速度の観点から、０．１質量部以上１０質量部以下であることが好ましい。 The amount of the polymerization reaction inhibitor charged (used amount) is preferably 0.1 part by mass or more and 10 parts by mass or less from the viewpoint of the polymerization rate with respect to 100 parts by mass of the total amount of the monomers.
＜連鎖移動剤＞
連鎖移動剤としては、特に限定されないが、硫黄元素を含む連鎖移動剤が挙げられ、より具体的には、ｔ−ドデシルメルカプタン、ｎ−ドデシルメルカプタン、等のアルカンチオール、メルカプトエタノール、メルカプトプロパノール等のチオアルキルアルコール、チオグリコール酸、チオプロピオン酸等のチオアルキルカルボン酸、チオグリコール酸オクチルエステル、チオプロピオン酸オクチルエステル等のチオカルボン酸アルキルエステル、ジメチルスルフィド、ジエチルスルフィド等のスルフィド等が挙げられる。また、ターピノーレン、ジペンテン、ｔ−テルピネン、四塩化炭素等のハロゲン化炭化水素が挙げられる。これらの連鎖移動剤は、１種を単独で、又は２種以上を組み合わせて用いてもよい。
<Chain transfer agent>
The chain transfer agent is not particularly limited, and examples thereof include a chain transfer agent containing a sulfur element, and more specifically, an alcoholic acid such as t-dodecyl mercaptan, n-dodecyl mercaptan, mercaptoethanol, mercaptopropanol and the like. Examples thereof include thioalkylcarboxylic acids such as thioalkyl alcohols, thioglycolic acids and thiopropionic acids, thiocarboxylic acid alkyl esters such as thioglycolic acid octyl esters and thiopropionic acid octyl esters, and sulfides such as dimethyl sulfide and diethyl sulfide. Further, halogenated hydrocarbons such as tarpinolene, dipentene, t-terpinene and carbon tetrachloride can be mentioned. These chain transfer agents may be used alone or in combination of two or more.
連鎖移動剤は、これらの中でも、連鎖移動速度が大きく、また共重合体の物性が優れる観点から、ｔ−ドデシルメルカプタンであることが好ましい。本実施形態の重合工程では、連鎖移動剤を、単量体と混合して反応系に仕込んでもよく、単独で所定の時期に所定量反応系に仕込んでもよい。これらの連鎖移動剤の仕込み量（使用量）は、単量体の総量１００質量部に対して、０．１質量部以上１０質量部以下であることが好ましい。仕込み量が０．１質量部以上であることにより、架橋剤とラテックスが反応しづらく、反応効率が低下する。仕込み量が１０質量部以下であることにより、架橋剤との反応速度を緩やかにできる。 Among these, the chain transfer agent is preferably t-dodecyl mercaptan from the viewpoint of high chain transfer rate and excellent physical properties of the copolymer. In the polymerization step of the present embodiment, the chain transfer agent may be mixed with the monomer and charged into the reaction system, or may be charged alone into the reaction system in a predetermined amount at a predetermined time. The amount of these chain transfer agents charged (used amount) is preferably 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total amount of the monomers. When the amount charged is 0.1 parts by mass or more, the cross-linking agent and the latex are difficult to react with each other, and the reaction efficiency is lowered. When the amount charged is 10 parts by mass or less, the reaction rate with the cross-linking agent can be slowed down.
本実施形態の重合工程（例えば、乳化重合による重合工程）において、さらに酸化還元触媒として、金属触媒、例えば、２価の鉄イオン、３価の鉄イオン、銅イオン等を共存させてもよい。 In the polymerization step of the present embodiment (for example, the polymerization step by emulsion polymerization), a metal catalyst such as divalent iron ion, trivalent iron ion, copper ion and the like may coexist as the oxidation-reduction catalyst.
さらに酸化還元触媒として、金属触媒、例えば、２価の鉄イオン、３価の鉄イオン、銅イオン等を共存させてもよい。 Further, as the redox catalyst, a metal catalyst such as divalent iron ion, trivalent iron ion, copper ion and the like may coexist.
本実施形態においては、必要に応じ各種重合調整剤をさらに添加することができる。例えば、ｐＨ調整剤として、水酸化ナトリウム、水酸化カリウム、水酸化アンモニウム、炭酸水素ナトリウム、炭酸ナトリウム、リン酸水素二ナトリウム等のｐＨ調整剤をさらに添加することができる。また、ジアミン四酢酸ナトリウム等の各種キレート剤等も重合調整剤としてさらに添加することもできる。ｐＨ調整剤の仕込み量（使用量）は、単量体の総量１００質量部に対して、０を超えて、１．０質量部以下であってもよい。 In the present embodiment, various polymerization modifiers can be further added as needed. For example, as a pH adjuster, a pH adjuster such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium hydrogen carbonate, sodium carbonate, disodium hydrogen phosphate and the like can be further added. Further, various chelating agents such as sodium diamine tetraacetate can be further added as a polymerization regulator. The amount of the pH adjuster charged (used amount) may be more than 0 and 1.0 part by mass or less with respect to 100 parts by mass of the total amount of the monomer.
また、上述した以外の添加剤としては、アルカリ感応ラテックス、ヘキサメタリン酸等の減粘剤、ポリビニルアルコール、カルボキシメチルセルロース等の水溶性高分子、増粘剤、各種老化防止剤、紫外線吸収剤、防腐剤、殺菌剤、消泡剤、ポリアクリル酸ナトリウム等の分散剤、耐水化剤、亜鉛華等の金属酸化物、滑剤、保水剤等の各種添加剤を添加してもよい。これらの添加剤の添加方法は、特に制限されず共重合体の重合時、重合後に関わらず添加することができる。 Additives other than those mentioned above include alkali-sensitive latex, thickeners such as hexametaphosphate, water-soluble polymers such as polyvinyl alcohol and carboxymethyl cellulose, thickeners, various anti-aging agents, ultraviolet absorbers, and preservatives. , Disinfectants, defoaming agents, dispersants such as sodium polyacrylate, water resistant agents, metal oxides such as zinc flower, lubricants, water retention agents and other various additives may be added. The method of adding these additives is not particularly limited, and the copolymer can be added at the time of polymerization or after the polymerization.
本実施形態の重合工程（例えば、乳化重合による重合工程）における重合温度は、例えば、６０〜１２０℃の範囲であり、レドックス重合法等を用いる場合には、より低い温度で重合を行ってもよい。 The polymerization temperature in the polymerization step of the present embodiment (for example, the polymerization step by emulsion polymerization) is, for example, in the range of 60 to 120 ° C., and when the redox polymerization method or the like is used, the polymerization can be carried out at a lower temperature. Good.
［塗膜］
本実施形態の塗膜は、前記水系組成物をイソシアネート系硬化剤によって硬化した塗膜である。イソシアネート系硬化剤は、水系組成物中に含有されていてもよいし、水系組成物とは別に準備されていてもよい。
[Coating film]
The coating film of the present embodiment is a coating film obtained by curing the aqueous composition with an isocyanate-based curing agent. The isocyanate-based curing agent may be contained in the water-based composition, or may be prepared separately from the water-based composition.
塗膜は、水系組成物を基材に塗布し、加熱し、乾燥することにより形成することができる。水系組成物がイソシアネート系硬化剤を含まない場合には、基材への塗布の前に、水系組成物をイソシアネート系硬化剤と混合することが好ましい。 The coating film can be formed by applying an aqueous composition to a base material, heating, and drying. When the aqueous composition does not contain an isocyanate-based curing agent, it is preferable to mix the aqueous composition with the isocyanate-based curing agent before coating on the substrate.
加熱温度は、特に限定されないが、例えば１００〜１５０℃としてもよい。加熱時間は、特に限定されないが、例えば１０分〜１時間としてもよい。 The heating temperature is not particularly limited, but may be, for example, 100 to 150 ° C. The heating time is not particularly limited, but may be, for example, 10 minutes to 1 hour.
乾燥温度は、特に限定されないが、例えば２０〜３０℃としてもよい。乾燥時間は、特に限定されないが、例えば１〜５日としてもよい。 The drying temperature is not particularly limited, but may be, for example, 20 to 30 ° C. The drying time is not particularly limited, but may be, for example, 1 to 5 days.
以下、本発明を実施例及び比較例を用いてさらに具体的に説明する。本発明は、以下の実施例によって何ら限定されるものではない。
なお、上述した各種パラメータは、特に断りのない限り、実施例に記載の測定方法に準じて測定される。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.
Unless otherwise specified, the various parameters described above are measured according to the measurement method described in the examples.
＜水系組成物の調製＞
（実施例１〜３）
撹拌装置と温度調節用ジャケットとを取り付けた耐圧反応容器に、表１に示す第１原料を表１に示す仕込み量にて仕込み、内温を８５℃に昇温した。次に、表１に示す第２原料を表１に示す仕込み量にて、５時間かけて一定の流速で仕込むとともに、表１に示す第３原料を表１に示す仕込み量にて６時間かけて一定の流速で仕込んだ。次に、温度を８５℃に１時間保って、重合反応を完了した。得られた水系組成物に水酸化ナトリムを加えてｐＨを７に調整し、スチームストリッピング法により未反応の単量体を除去し、２００メッシュの金網で濾過し、固形分濃度を４０質量％に調整した。水系組成物は分散液の形態で得られた。
<Preparation of aqueous composition>
(Examples 1 to 3)
The first raw material shown in Table 1 was charged in a pressure-resistant reaction vessel equipped with a stirrer and a temperature control jacket in the amount shown in Table 1, and the internal temperature was raised to 85 ° C. Next, the second raw material shown in Table 1 is charged at a constant flow rate over 5 hours at the charging amount shown in Table 1, and the third raw material shown in Table 1 is charged at the charging amount shown in Table 1 over 6 hours. It was charged at a constant flow rate. Next, the temperature was maintained at 85 ° C. for 1 hour to complete the polymerization reaction. Natrim hydroxide was added to the obtained aqueous composition to adjust the pH to 7, unreacted monomers were removed by a steam stripping method, and the mixture was filtered through a 200 mesh wire mesh to adjust the solid content concentration to 40% by mass. Adjusted to. The aqueous composition was obtained in the form of a dispersion.
（比較例１及び２）
撹拌装置と温度調節用ジャケットとを取り付けた耐圧反応容器に、表１に示す第１原料を表１に示す仕込み量にて仕込み、内温を８５℃に昇温した。次に、表１に示す第２原料を表１に示す仕込み量にて、５時間かけて一定の流速で仕込むとともに、表１に示す第３原料を表１に示す仕込み量にて６時間かけて一定の流速で仕込んだ。次に、温度を８５℃に１時間保って、重合反応を完了した。得られた水系組成物に水酸化ナトリムを加えてｐＨを７に調整し、スチームストリッピング法により未反応の単量体を除去し、２００メッシュの金網で濾過し、固形分濃度を５０質量％に調整した。水系組成物は分散液の形態で得られた。
(Comparative Examples 1 and 2)
The first raw material shown in Table 1 was charged in a pressure-resistant reaction vessel equipped with a stirrer and a temperature control jacket in the amount shown in Table 1, and the internal temperature was raised to 85 ° C. Next, the second raw material shown in Table 1 is charged at a constant flow rate over 5 hours at the charging amount shown in Table 1, and the third raw material shown in Table 1 is charged at the charging amount shown in Table 1 over 6 hours. It was charged at a constant flow rate. Next, the temperature was maintained at 85 ° C. for 1 hour to complete the polymerization reaction. Natrim hydroxide was added to the obtained aqueous composition to adjust the pH to 7, unreacted monomers were removed by the steam stripping method, and the mixture was filtered through a 200 mesh wire mesh to adjust the solid content concentration to 50% by mass. Adjusted to. The aqueous composition was obtained in the form of a dispersion.
＜粘度＞
（配合物の調製）
１５質量％に調整したポリビニルアルコール（株式会社クラレ製、ポバール２１７）水溶液４０質量部、炭酸カルシウム４０質量部、及び前記水系組成物４０質量部を混合撹拌し、ベースコンパウンドを作成した。次いで、このベースコンパウンドに硬化剤としてジフェニルメタン−４，４’−ジイソシアネート１２質量部を添加し、スリーワンモーターを使用し、５００回転で２分間攪拌した。
<Viscosity>
(Preparation of formulation)
A base compound was prepared by mixing and stirring 40 parts by mass of an aqueous solution of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval 217) adjusted to 15% by mass, 40 parts by mass of calcium carbonate, and 40 parts by mass of the aqueous composition. Next, 12 parts by mass of diphenylmethane-4,4'-diisocyanate was added to this base compound as a curing agent, and the mixture was stirred at 500 rpm for 2 minutes using a three-one motor.
（粘度測定）
攪拌終了後１分以内の粘度、及び攪拌終了後から２５℃で３０分放置した後の粘度を、Ｂ型粘度計（ＴＶＢ−１０型）及びローターＮｏ．Ｈ７のローターを用いて、回転速度６０ｒｐｍ及び測定温度２５℃の条件で測定した。結果を表２に示す。
(Viscosity measurement)
The viscosity within 1 minute after the completion of stirring and the viscosity after being left at 25 ° C. for 30 minutes after the completion of stirring were determined by the B-type viscometer (TVB-10 type) and the rotor No. The measurement was performed using a rotor of H7 under the conditions of a rotation speed of 60 rpm and a measurement temperature of 25 ° C. The results are shown in Table 2.
＜接触角＞
前記粘度の測定時と同様、配合物を調整し、２０μｍの厚さになるようにポリプロピレンシートに塗布した。その後、２５℃で３日間乾燥し、塗膜を得た。この塗膜に水滴を１滴たらした際の接触角をＫＹＯＷＡ製の接触角計ＰＣＡ−１によって測定した。結果を表３に示す。
<Contact angle>
As in the case of measuring the viscosity, the formulation was adjusted and applied to a polypropylene sheet to a thickness of 20 μm. Then, it was dried at 25 degreeC for 3 days to obtain a coating film. The contact angle when one drop of water was dropped on this coating film was measured with a contact angle meter PCA-1 manufactured by KYOWA. The results are shown in Table 3.
＜平均粒子経＞
ブラウン運動している微粒子に光を当て、粒子から戻ってくる光（後方散乱光）の振動数（光の周波数）の変化量から、微粒子の粒子径を求める方法で体積平均粒子径（ｎｍ）を測定した。測定装置はマイクロトラックＵＰＡ１５０（日機装株式会社）を用いた。
<Average particle diameter>
Volume average particle diameter (nm) by shining light on Brownian-motion fine particles and determining the particle size of the fine particles from the amount of change in the frequency (light frequency) of the light (backscattered light) returning from the particles. Was measured. A microtrack UPA150 (Nikkiso Co., Ltd.) was used as the measuring device.
＜ゲル分率＞
テフロン（登録商標）シート上で前記水系組成物サンプル約１ｇを１３０℃で３０分乾燥した。乾燥したサンプルを約０．５ｇ精秤し、３０ｍｌのトルエンが入った容器に入れ、振とう器で３時間振とうした。振とう後のトルエン分散液を３２５メッシュのステンレス金網で濾過し、濾過残さ量を１３０℃で１時間乾燥して測定した。トルエン不溶分は乾燥サンプル重量に対する濾過残さ乾燥重量の割合（重量％）から求めた。
<Gel fraction>
About 1 g of the aqueous composition sample was dried at 130 ° C. for 30 minutes on a Teflon (registered trademark) sheet. About 0.5 g of the dried sample was precisely weighed, placed in a container containing 30 ml of toluene, and shaken with a shaker for 3 hours. The toluene dispersion after shaking was filtered through a 325 mesh stainless wire mesh, and the amount of residual filtration was measured by drying at 130 ° C. for 1 hour. The toluene insoluble content was determined from the ratio (% by weight) of the dry weight of the filtration residue to the weight of the dry sample.
＜ガラス転移温度（Ｔｇ）＞
水系組成物を１００℃で１時間乾燥を行い、フィルムを作成した。このフィルムを高感度示差走査熱量計（エスアイアイ・ナノテクノロジー株式会社製ＤＳＣ−７０２０）を用いて、温度−７５℃から＋１１５℃まで、昇温速度１５℃／ｍｉｎで測定した。ガラス転移温度は、ＤＳＣ曲線を更に温度で微分した、ＤＤＳＣ曲線のピーク位置をもってガラス転移温度とした。
<Glass transition temperature (Tg)>
The aqueous composition was dried at 100 ° C. for 1 hour to prepare a film. This film was measured using a high-sensitivity differential scanning calorimeter (DSC-7020 manufactured by SII Nanotechnology Co., Ltd.) from a temperature of −75 ° C. to + 115 ° C. at a heating rate of 15 ° C./min. The glass transition temperature was defined as the peak position of the DDSC curve, which was obtained by further differentiating the DSC curve with temperature.
Claims (8)
前記水系組成物と炭酸カルシウムとポリビニルアルコールとの混合物に、ジフェニルメタン−４，４’−ジイソシアネートを添加し３０分放置した後の粘度が、添加直後の粘度の５．８倍以下となる、前記水系組成物。 An aqueous composition containing a copolymer.
The viscosity of the mixture of the aqueous composition, calcium carbonate and polyvinyl alcohol after adding diphenylmethane-4,4'-diisocyanate and leaving it for 30 minutes is 5.8 times or less the viscosity immediately after the addition. Composition.
１０質量部以上３５質量部以下の水酸基含有不飽和単量体単位（Ａ）、
１０質量部以上６５質量部以下の脂肪族共役ジエン系単量体単位（Ｂ）、及び
０質量部以上７５質量部以下の重合性不飽和単量体単位（Ｃ）、
を有し、
前記重合性不飽和単量体単位（Ｃ）が、前記水酸基含有不飽和単量体単位（Ａ）及び前記脂肪族共役ジエン系単量体単位（Ｂ）と異なる、
請求項１に記載の水系組成物。 When the total amount of the monomer units constituting the copolymer is 100 parts by mass, the copolymer
Hydroxy group-containing unsaturated monomer unit (A) of 10 parts by mass or more and 35 parts by mass or less,
Aliphatic conjugated diene monomer unit (B) of 10 parts by mass or more and 65 parts by mass or less, and polymerizable unsaturated monomer unit (C) of 0 parts by mass or more and 75 parts by mass or less.
Have,
The polymerizable unsaturated monomer unit (C) is different from the hydroxyl group-containing unsaturated monomer unit (A) and the aliphatic conjugated diene-based monomer unit (B).
The aqueous composition according to claim 1.
水酸基含有不飽和単量体及び脂肪族共役ジエン系単量体を重合する重合工程を含み、
前記重合工程を実施する前に、前記製造方法で使用される水酸基含有不飽和単量体の全量が前記脂肪族共役ジエン系単量体と混合される、前記製造方法。 The method for producing an aqueous composition according to any one of claims 1 to 5.
Including a polymerization step of polymerizing a hydroxyl group-containing unsaturated monomer and an aliphatic conjugated diene-based monomer.
The production method, wherein the total amount of the hydroxyl group-containing unsaturated monomer used in the production method is mixed with the aliphatic conjugated diene-based monomer before carrying out the polymerization step.
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| JP2019172719A (en) * | 2018-03-27 | 2019-10-10 | 旭化成株式会社 | Copolymer latex for aqueous adhesive and manufacturing method therefor |
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| JPH0718003A (en) * | 1993-07-02 | 1995-01-20 | Japan Synthetic Rubber Co Ltd | Production of latex |
| JPH07268037A (en) * | 1994-04-01 | 1995-10-17 | Asahi Chem Ind Co Ltd | Copolymer emulsion and its production and use thereof |
| JP2003082309A (en) * | 2001-09-10 | 2003-03-19 | Asahi Kasei Corp | Latex for aqueous vinylurethane adhesive |
| JP2005213373A (en) * | 2004-01-29 | 2005-08-11 | Asahi Kasei Chemicals Corp | Copolymer latex for aqueous vinylurethane adhesive |
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