JP5970350B2 - Anti-fogging agent - Google Patents
Anti-fogging agent Download PDFInfo
- Publication number
- JP5970350B2 JP5970350B2 JP2012253723A JP2012253723A JP5970350B2 JP 5970350 B2 JP5970350 B2 JP 5970350B2 JP 2012253723 A JP2012253723 A JP 2012253723A JP 2012253723 A JP2012253723 A JP 2012253723A JP 5970350 B2 JP5970350 B2 JP 5970350B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- antifogging agent
- antifogging
- monomer unit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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- 238000006116 polymerization reaction Methods 0.000 claims description 33
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 11
- 125000004423 acyloxy group Chemical group 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
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- 238000000034 method Methods 0.000 description 19
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
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- 235000014113 dietary fatty acids Nutrition 0.000 description 2
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- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
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- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
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- SYYDEXILBJXXIA-UHFFFAOYSA-N trimethoxy(pent-4-enyl)silane Chemical compound CO[Si](OC)(OC)CCCC=C SYYDEXILBJXXIA-UHFFFAOYSA-N 0.000 description 2
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- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 150000001299 aldehydes Chemical class 0.000 description 1
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- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- WXPWPYISTQCNDP-UHFFFAOYSA-N oct-7-en-1-ol Chemical compound OCCCCCCC=C WXPWPYISTQCNDP-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000765 poly(2-oxazolines) Polymers 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 description 1
- ZQYKGADTDCTWSZ-UHFFFAOYSA-N trimethyl-[(prop-2-enoylamino)methyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CNC(=O)C=C ZQYKGADTDCTWSZ-UHFFFAOYSA-N 0.000 description 1
- CCVMLEHYQVSFOM-UHFFFAOYSA-N trimethyl-[2-(prop-2-enoylamino)ethyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCNC(=O)C=C CCVMLEHYQVSFOM-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明はビニルアルコール系重合体を含有する防曇剤に関する。 The present invention relates to an antifogging agent containing a vinyl alcohol polymer.
ポリビニルアルコールに代表されるビニルアルコール系重合体（以下、「ＰＶＡ」と略記することがある。）は、水溶性の合成高分子として知られており、合成繊維であるビニロンの原料、紙加工剤、繊維加工剤、接着剤、乳化重合及び懸濁重合用の安定剤、無機物のバインダー、フィルムなどの用途に広く用いられている。特に、ＰＶＡは他の水溶性合成高分子と比べて強度特性及び造膜性に優れており、この特性を生かして、例えばガラス、金属等の基材の表面に塗工される防曇剤として重用されている。 A vinyl alcohol polymer represented by polyvinyl alcohol (hereinafter sometimes abbreviated as “PVA”) is known as a water-soluble synthetic polymer, and is a raw material for vinylon which is a synthetic fiber, a paper processing agent. It is widely used for fiber processing agents, adhesives, stabilizers for emulsion polymerization and suspension polymerization, inorganic binders, films and the like. In particular, PVA is superior in strength properties and film-forming properties compared to other water-soluble synthetic polymers, and as an antifogging agent applied to the surface of a substrate such as glass or metal, taking advantage of these properties. It is heavily used.
このようなＰＶＡの特性をさらに高めるために、各種変性がなされたＰＶＡが開発されている。変性ＰＶＡの一つとして、シリル基含有ＰＶＡが挙げられる。このシリル基含有ＰＶＡは、耐水性及び無機物等に対する接着性が高い。しかし、シリル基含有ＰＶＡは、（ａ）水溶液を調製する際に水酸化ナトリウム等のアルカリや酸を添加しなければ、十分に溶解しにくいこと、（ｂ）調製された水溶液の粘度安定性が低下すること、（ｃ）無機物等を含有する塗膜を形成させた場合、得られる塗膜の耐水性と無機物等に対する接着性とを同時に満足させることが困難であること等の不都合がある。そのため、上記シリル基含有ＰＶＡを含有する防曇剤は、得られる塗膜の防曇性、防曇効果の持続性（以下、「持続的防曇性」とも称する）及び基材への密着性等を同時に満足させることが困難となる。 In order to further enhance the properties of such PVA, PVA with various modifications has been developed. As one of the modified PVA, silyl group-containing PVA can be mentioned. This silyl group-containing PVA has high water resistance and high adhesion to inorganic substances. However, the silyl group-containing PVA is (a) difficult to dissolve unless an alkali or acid such as sodium hydroxide is added when preparing an aqueous solution, and (b) the viscosity stability of the prepared aqueous solution is low. In the case where a coating film containing (c) an inorganic substance or the like is formed, there are inconveniences such as difficulty in simultaneously satisfying the water resistance of the resulting coating film and the adhesion to the inorganic substance. Therefore, the antifogging agent containing the silyl group-containing PVA is antifogging property of the obtained coating film, durability of the antifogging effect (hereinafter also referred to as “sustained antifogging property”) and adhesion to the substrate. It becomes difficult to satisfy these simultaneously.
そこで、粘度平均重合度（Ｐ）とシリル基を有する単量体単位の含有率（Ｓ：モル％）との積（Ｐ×Ｓ）を一定範囲内とすることなどにより、水溶性等が高められたシリル基含有ＰＶＡ（特開２００４−４３６４４号公報参照）が提案されている。しかし、このシリル基含有ＰＶＡにおいては、上記積（Ｐ×Ｓ）の上限が３７０とされており、シリル基を有する単量体単位の含有率を増やしてシリル基含有ＰＶＡとしての特性を高めることと、水溶性等を高めることとのトレードオフの関係が解消されてはいない。すなわち、上記特開２００４−４３６４４号公報の段落０００９に記載のように、積（Ｐ×Ｓ）が３７０以上の場合には、シリル基含有ＰＶＡの水溶液を調製する際にアルカリや酸を添加しなければ溶解できない場合があるという取扱上の不都合を有している。つまり、上記シリル基含有ＰＶＡも、上述の不都合を十分に解決したものとはいえない。 Therefore, water solubility and the like are improved by setting the product (P × S) of the viscosity average degree of polymerization (P) and the content of the monomer unit having a silyl group (S: mol%) within a certain range. A silyl group-containing PVA (see Japanese Patent Application Laid-Open No. 2004-43644) has been proposed. However, in this silyl group-containing PVA, the upper limit of the product (P × S) is set to 370, and the content of the monomer unit having a silyl group is increased to enhance the characteristics as the silyl group-containing PVA. And the trade-off relationship between improving water solubility and the like has not been resolved. That is, as described in paragraph 0009 of JP 2004-43644 A, when the product (P × S) is 370 or more, an alkali or an acid is added when preparing an aqueous solution of silyl group-containing PVA. Otherwise, there is a disadvantage in handling that it may not be dissolved. That is, it cannot be said that the silyl group-containing PVA sufficiently solves the above-mentioned disadvantages.
本発明は、上述のような事情に基づいてなされたものであり、防曇性、持続的防曇性及び基材への密着性に優れる塗膜を得ることができ、取扱性及び粘度安定性も十分な防曇剤の提供を目的とする。 The present invention has been made based on the above circumstances, and can provide a coating film having excellent antifogging properties, continuous antifogging properties, and adhesion to a substrate, handling properties and viscosity stability. Is intended to provide a sufficient antifogging agent.
上記課題を解決するためになされた発明は、
下記式（１）で表される基を有する単量体単位を含み、下記式（Ｉ）を満たすビニルアルコール系重合体を含有する防曇剤である。
The invention made to solve the above problems is
The antifogging agent contains a vinyl alcohol polymer that includes a monomer unit having a group represented by the following formula (1) and satisfies the following formula (I).
３７０≦Ｐ×Ｓ≦６，０００ ・・・（Ｉ）
Ｐ：粘度平均重合度
Ｓ：上記単量体単位の含有率（モル％）
370 ≦ P × S ≦ 6,000 (I)
P: Viscosity average degree of polymerization S: Content of the monomer unit (mol%)
当該防曇剤に含有されるＰＶＡは、上記式（１）で表される基を有する単量体単位を含み、シリル基が炭素数３以上のアルキレン基を介して主鎖と連結した構造を有している。このため、当該防曇剤は、含まれるＰＶＡのシリル基の変性量を高めても、中性領域における水溶性が高いため取扱性もよく、粘度安定性の低下が抑えられる。また、当該防曇剤によれば、含まれるＰＶＡの粘度平均重合度（Ｐ）と上記単量体単位の含有率（Ｓ）との積（Ｐ×Ｓ）が上記範囲であるため、シリル基変性量を高めることができ、防曇性、持続的防曇性及び基材への密着性に優れる塗膜を得ることができる。 The PVA contained in the antifogging agent has a structure in which a monomer unit having a group represented by the above formula (1) is included, and a silyl group is connected to a main chain via an alkylene group having 3 or more carbon atoms. Have. For this reason, even if it raises the modification | denaturation amount of the silyl group of PVA contained, since the water solubility in a neutral region is high, the said antifogging agent has good handleability, and the fall of viscosity stability is suppressed. Further, according to the antifogging agent, since the product (P × S) of the viscosity average polymerization degree (P) of the contained PVA and the content (S) of the monomer unit is in the above range, the silyl group The amount of modification can be increased, and a coating film excellent in antifogging property, continuous antifogging property and adhesion to a substrate can be obtained.
上記ＰＶＡが、下記式（ＩＩ）及び（ＩＩＩ）をさらに満たすことが好ましい。
２００≦Ｐ≦４，０００ ・・・（ＩＩ）
０．１≦Ｓ≦１０ ・・・（ＩＩＩ）
Ｐ：粘度平均重合度
Ｓ：上記単量体単位の含有率（モル％）
It is preferable that the PVA further satisfies the following formulas (II) and (III).
200 ≦ P ≦ 4,000 (II)
0.1 ≦ S ≦ 10 (III)
P: Viscosity average degree of polymerization S: Content of the monomer unit (mol%)
このように上記ＰＶＡの粘度平均重合度（Ｐ）及び上記単量体単位の含有率（Ｓ）を上記範囲とすることで、水溶性及び粘度安定性が高まり、得られる塗膜の防曇性、持続的防曇性及び基材への密着性をより高めることができる。 Thus, by setting the viscosity average degree of polymerization (P) of the PVA and the content (S) of the monomer unit in the above ranges, the water solubility and viscosity stability are improved, and the resulting coating film has an antifogging property. Further, the continuous antifogging property and the adhesion to the substrate can be further improved.
上記式（１）におけるｎは６〜２０の整数であることが好ましい。ｎの値を上記範囲とすることで、当該防曇剤の諸性能をより高めることができる。 In the above formula (1), n is preferably an integer of 6 to 20. By setting the value of n within the above range, various performances of the antifogging agent can be further enhanced.
上記単量体単位は下記式（２）で表されることが好ましい。
上記単量体単位が上記式（２）で表される構造を有することで、当該防曇剤の諸性能をより高めることができる。 When the monomer unit has a structure represented by the formula (2), various performances of the antifogging agent can be further improved.
上記式（２）におけるＸは下記式（３）で表されることが好ましい。
−ＣＯ−ＮＲ６−＊・・・（３）
（式（３）中、Ｒ６は、水素原子又は炭素数１〜５のアルキル基である。＊は、上記式（１）で表される基との結合箇所を示す。）
X in the above formula (2) is preferably represented by the following formula (3).
-CO-NR 6- * (3)
(In the formula (3), R 6 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. * Indicates a bonding position with the group represented by the above formula (1).)
このように上記単量体単位がシリル基と離れた位置にアミド構造を有することで、シリル基に由来する性能を維持しつつ、水溶性及び粘度安定性等をより高めることができる。 Thus, when the monomer unit has an amide structure at a position away from the silyl group, water solubility and viscosity stability can be further improved while maintaining the performance derived from the silyl group.
上記式（３）におけるＲ６は水素原子であり、上記式（２）におけるｎは３〜１２の整数であることが好ましい。上記単量体単位をこのような構造とすることで、上記ＰＶＡの水溶性や粘度安定性が高まり、当該防曇剤により得られる塗膜の諸特性も高めることができ、また、上記ＰＶＡの製造を容易に行うことができる。 R 6 in the above formula (3) is a hydrogen atom, and n in the above formula (2) is preferably an integer of 3 to 12. By setting the monomer unit to such a structure, the water solubility and viscosity stability of the PVA are increased, and various properties of the coating film obtained by the antifogging agent can be enhanced. Manufacture can be performed easily.
当該防曇剤は、無機物をさらに含有することが好ましい。当該防曇剤が無機物をさらに含有することで、得られる塗膜の耐水性を高めることができ、その結果、塗膜の防曇性、持続的防曇性及び基材への密着性をさらに高めることができる。 The antifogging agent preferably further contains an inorganic substance. When the antifogging agent further contains an inorganic substance, the water resistance of the obtained coating film can be increased, and as a result, the antifogging property of the coating film, the continuous antifogging property, and the adhesion to the substrate are further increased. Can be increased.
本発明の透明部材は、
透明な基材と
当該防曇剤を用い、この基材表面に積層される防曇層と
を備える。当該透明部材は、当該防曇剤を用いて積層される防曇層を有するため、防曇性及び持続的防曇性に優れる。従って、当該透明部材は、窓ガラス、眼鏡用レンズ、浴室の鏡などの用途に好適に用いられる。
The transparent member of the present invention is
Using a transparent base material and the said antifogging agent, the antifogging layer laminated | stacked on this base material surface is provided. Since the transparent member has an anti-fogging layer laminated using the anti-fogging agent, it is excellent in anti-fogging property and continuous anti-fogging property. Therefore, the said transparent member is used suitably for uses, such as a window glass, a lens for spectacles, and a bathroom mirror.
以上説明したように、本発明の防曇剤は、十分な取扱性及び粘度安定性を有し、得られる塗膜の防曇性、持続的防曇性及び基材への密着性に優れる。従って、当該防曇剤を用いて基材表面に積層される防曇層を備える透明部材は、防曇性及び持続的防曇性に優れる。 As described above, the antifogging agent of the present invention has sufficient handleability and viscosity stability, and is excellent in antifogging property, continuous antifogging property and adhesion to a substrate of the resulting coating film. Therefore, a transparent member provided with an antifogging layer laminated on the substrate surface using the antifogging agent is excellent in antifogging properties and continuous antifogging properties.
以下、本発明の防曇剤の実施の形態について詳説する。 Hereinafter, embodiments of the antifogging agent of the present invention will be described in detail.
＜防曇剤＞
本発明の防曇剤は、以下に詳説するＰＶＡを含有する。
<Anti-fogging agent>
The antifogging agent of this invention contains PVA explained in full detail below.
＜ＰＶＡ＞
上記ＰＶＡは、上記式（１）で表される基を有する単量体単位を含む。すなわち、上記ＰＶＡは、上記式（１）で表される基を有する単量体単位とビニルアルコール単位（−ＣＨ２−ＣＨＯＨ−）とを含む共重合体であり、さらに他の単量体単位を有してもよい。
<PVA>
The PVA includes a monomer unit having a group represented by the formula (1). That is, the PVA is a copolymer containing a monomer unit having a group represented by the formula (1) and a vinyl alcohol unit (—CH 2 —CHOH—), and further another monomer unit. You may have.
上記式（１）中、Ｒ１は、水素原子又は炭素数１〜５のアルキル基である。上記アルキル基としては、メチル基、エチル基、プロピル基等が挙げられる。 In the above formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.
Ｒ２は、アルコキシル基、アシロキシル基又はＯＭで表される基である。Ｍは、水素原子、アルカリ金属又はアンモニウム基（＋ＮＨ４）である。上記アルコキシル基としては、メトキシ基、エトキシ基等が挙げられる。上記アシロキシル基としては、アセトキシ基、プロピオニルオキシ基等が挙げられる。上記アルカリ金属としては、ナトリウム、カリウム等が挙げられる。Ｒ２で表されるこれらの基の中でも、アルコキシル基又はＯＭで表される基が好ましく、炭素数１〜５のアルコキシル基、及びＭが水素原子若しくはアルカリ金属であるＯＭで表される基がより好ましく、メトキシ基、エトキシ基及びＭがナトリウム若しくはカリウムであるＯＭで表される基がさらに好ましい。 R 2 is a group represented by an alkoxyl group, an acyloxyl group, or OM. M is a hydrogen atom, an alkali metal, or an ammonium group ( + NH 4 ). Examples of the alkoxyl group include a methoxy group and an ethoxy group. Examples of the acyloxyl group include an acetoxy group and a propionyloxy group. Examples of the alkali metal include sodium and potassium. Among these groups represented by R 2 , an alkoxyl group or a group represented by OM is preferable, an alkoxyl group having 1 to 5 carbon atoms, and a group represented by OM in which M is a hydrogen atom or an alkali metal. More preferably, a methoxy group, an ethoxy group, and a group represented by OM in which M is sodium or potassium are more preferable.
Ｒ３及びＲ４は、それぞれ独立して、水素原子又はアルキル基である。このアルキル基としては、上述した炭素数１〜５のアルキル基等が挙げられる。Ｒ３及びＲ４としては、水素原子又はメチル基が好ましい。 R 3 and R 4 are each independently a hydrogen atom or an alkyl group. Examples of the alkyl group include the above-described alkyl groups having 1 to 5 carbon atoms. R 3 and R 4 are preferably a hydrogen atom or a methyl group.
Ｒ１〜Ｒ４で表されるアルキル基、アルコキシル基及びアシロキシル基が有する水素原子は、酸素原子又は窒素原子を含有する置換基で置換されていてもよい。酸素原子を含有する置換基としては、アルコキシル基、アシロキシル基等が挙げられる。また、窒素原子を含有する置換基としては、アミノ基、シアノ基等が挙げられる。 The hydrogen atom which the alkyl group, alkoxyl group, and acyloxyl group represented by R 1 to R 4 have may be substituted with a substituent containing an oxygen atom or a nitrogen atom. Examples of the substituent containing an oxygen atom include an alkoxyl group and an acyloxyl group. In addition, examples of the substituent containing a nitrogen atom include an amino group and a cyano group.
なお、Ｒ１〜Ｒ４がそれぞれ複数存在する場合、複数存在する各Ｒ１〜Ｒ４は、独立して上記定義を満たす。 In the case where R 1 to R 4 is present in plural, each R 1 to R 4 that there are two or more, independently meets the above definition.
ｍは、０〜２の整数であるが、０が好ましい。ｍが０である、すなわち、上記単量体単位が、３つのＲ２基を有することで、変性による効果をより高めることができる。 m is an integer of 0 to 2, and 0 is preferable. When m is 0, that is, the monomer unit has three R 2 groups, the effect of modification can be further enhanced.
ｎは、３以上の整数である。ｎの上限としては、特に制限されないが、２０が好ましく、１５がより好ましく、１２がさらに好ましい。ｎの下限としては、４が好ましく、６がより好ましく、８がさらに好ましい。上記ＰＶＡは、上記式（１）中のｎが３以上、すなわちシリル基が炭素数３以上のアルキレン基を介して主鎖と連結した構造を有していることで、シリル基の変性量を高めても、水溶性及び粘度安定性の低下が抑えられる。このような効果が発現する理由は十分解明されてはいないが、例えば、疎水性を示す炭素数３以上のアルキレン基が、水溶液中において、Ｓｉ−Ｒ２の加水分解速度を低下させ、反応を阻害させるためであると推測される。 n is an integer of 3 or more. The upper limit of n is not particularly limited, but 20 is preferable, 15 is more preferable, and 12 is more preferable. As a lower limit of n, 4 is preferable, 6 is more preferable, and 8 is more preferable. The PVA has a structure in which n in the formula (1) is 3 or more, that is, the silyl group is connected to the main chain via an alkylene group having 3 or more carbon atoms, so that the amount of modification of the silyl group can be reduced. Even if it raises, the fall of water solubility and viscosity stability is suppressed. The reason why such an effect is not fully elucidated has been elucidated, but for example, an alkylene group having 3 or more carbon atoms exhibiting hydrophobicity reduces the hydrolysis rate of Si—R 2 in an aqueous solution, thereby causing a reaction. It is presumed to be for inhibiting.
上記単量体単位の具体的構造は、上記式（１）で表される基を有する限り特に限定されないが、上記式（２）で表されることが好ましい。 The specific structure of the monomer unit is not particularly limited as long as it has a group represented by the above formula (1), but is preferably represented by the above formula (2).
式（２）中、Ｒ１〜Ｒ４、ｍ及びｎの定義は、式（１）と同様である。また、これらの好ましい基又は数値範囲も同様である。 In formula (2), the definitions of R 1 to R 4 , m and n are the same as in formula (1). The same applies to these preferred groups or numerical ranges.
Ｘは直接結合、２価の炭化水素基又は酸素原子若しくは窒素原子を含む２価の有機基である。上記単量体単位が上記式（２）で表される構造を有することで、水溶性及び粘度安定性、並びに得られる塗膜の防曇性、持続的防曇性及び基材への密着性をより高めることができる。 X is a direct bond, a divalent hydrocarbon group, or a divalent organic group containing an oxygen atom or a nitrogen atom. By having the structure represented by the above formula (2), the monomer unit has water solubility and viscosity stability, and anti-fogging property, continuous anti-fogging property and adhesion to a substrate of the resulting coating film. Can be further enhanced.
上記２価の炭化水素基としては、炭素数１〜１０の２価の脂肪族炭化水素基、炭素数６〜１０の２価の芳香族炭化水素基等が挙げられる。上記炭素数１〜１０の脂肪族炭化水素基としては、メチレン基、エチレン基、プロピレン基等が挙げられる。上記炭素数６〜１０の２価の芳香族炭化水素基としては、フェニレン基等が挙げられる。上記酸素原子を含む２価の有機基としては、エーテル基、エステル基、カルボニル基、アミド基、及びこれらの基と２価の炭化水素基とが連結した基等が挙げられる。上記窒素原子を含む２価の有機基としては、イミノ基、アミド基、及びこれらの基と２価の炭化水素基とが連結した基等が挙げられる。 Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms. Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms include a methylene group, an ethylene group, and a propylene group. A phenylene group etc. are mentioned as said C6-C10 bivalent aromatic hydrocarbon group. Examples of the divalent organic group containing an oxygen atom include ether groups, ester groups, carbonyl groups, amide groups, and groups in which these groups are connected to a divalent hydrocarbon group. Examples of the divalent organic group containing a nitrogen atom include an imino group, an amide group, and a group in which these groups are connected to a divalent hydrocarbon group.
上記Ｘで表される基の中でも、酸素原子又は窒素原子を含む２価の有機基が好ましく、アミド基を含む基がより好ましく、−ＣＯ−ＮＲ６−＊（Ｒ６は、水素原子又は炭素数１〜５のアルキル基である。＊は、上記式（１）で表される基との結合箇所を示す。）で表される基であることがさらに好ましい。このように上記単量体単位がシリル基と離れた位置に極性構造、好ましくはアミド構造を有することで、シリル基に由来する性能を維持しつつ、水溶性や粘度安定性等をより高めることができる。なお、上記Ｒ６としては、上記機能をより高めたり、当該ＰＶＡの製造を容易に行うことができる点から、水素原子が好ましい。 Among the groups represented by X, a divalent organic group containing an oxygen atom or a nitrogen atom is preferable, a group containing an amide group is more preferable, and —CO—NR 6 — * (R 6 is a hydrogen atom or a carbon atom) It is an alkyl group of formulas 1 to 5. * is more preferably a group represented by the bonding site with the group represented by the above formula (1). In this way, the monomer unit has a polar structure, preferably an amide structure, at a position away from the silyl group, so that the performance derived from the silyl group is maintained and the water solubility and viscosity stability are further improved. Can do. As the above R 6, or more increase the above-mentioned function, from the viewpoint of the production of the PVA can be easily performed, a hydrogen atom is preferable.
Ｒ５は、水素原子又はメチル基である。 R 5 is a hydrogen atom or a methyl group.
上記単量体単位としては、下記式（４）で表されるものがさらに好ましい。 As said monomer unit, what is represented by following formula (4) is still more preferable.
式（４）中、Ｒ１、Ｒ２、Ｒ５、Ｘ及びｍの定義は、上記式（２）と同様である。また、これらの好ましい基又は数値範囲も同様である。 In the formula (4), the definitions of R 1 , R 2 , R 5 , X and m are the same as those in the above formula (2). The same applies to these preferred groups or numerical ranges.
上記式（４）中、Ｒ３’及びＲ４’は、それぞれ独立して、水素原子又はアルキル基である。このアルキル基としては、上述した炭素数１〜５のアルキル基が挙げられる。Ｒ３’及びＲ４’としては、水素原子又はメチル基が好ましく、水素原子がより好ましい。Ｒ３’及びＲ４’で表されるアルキル基が有する水素原子は、酸素原子又は窒素原子を含有する置換基で置換されていてもよい。酸素原子を含有する置換基としては、アルコキシル基、アシロキシル基等が挙げられる。また、窒素原子を含有する置換基としては、アミノ基、シアノ基等が挙げられる。なお、Ｒ３’及びＲ４’がそれぞれ複数存在する場合、複数存在する各Ｒ３’及びＲ４’は、独立して上記定義を満たす。 In the above formula (4), R 3 ′ and R 4 ′ are each independently a hydrogen atom or an alkyl group. As this alkyl group, the C1-C5 alkyl group mentioned above is mentioned. R 3 ′ and R 4 ′ are preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. The hydrogen atom contained in the alkyl group represented by R 3 ′ and R 4 ′ may be substituted with a substituent containing an oxygen atom or a nitrogen atom. Examples of the substituent containing an oxygen atom include an alkoxyl group and an acyloxyl group. In addition, examples of the substituent containing a nitrogen atom include an amino group and a cyano group. When there are a plurality of R 3 ′ and R 4 ′, a plurality of R 3 ′ and R 4 ′ satisfy the above definition independently.
上記式（４）中、ｎ’は、１以上の整数である。ｎ’の上限としては、特に制限されないが、１８が好ましく、１３がより好ましく、１０がさらに好ましい。ｎ’の下限としては、２が好ましく、４がより好ましく、６がさらに好ましい。 In the above formula (4), n ′ is an integer of 1 or more. The upper limit of n 'is not particularly limited, but 18 is preferable, 13 is more preferable, and 10 is more preferable. As a lower limit of n ′, 2 is preferable, 4 is more preferable, and 6 is more preferable.
上記単量体単位が、上記式（４）で表される場合、当該防曇剤の諸機能をより効果的に発現させることができる。この理由も定かではないが、水溶液中においてＳｉ−Ｒ２の加水分解速度を低下させ、反応を阻害させるという上述した機能がより効果的に発揮されるためと推測される。 When the monomer unit is represented by the above formula (4), various functions of the antifogging agent can be expressed more effectively. The reason for this is not clear, but it is presumed that the above-described function of reducing the hydrolysis rate of Si—R 2 and inhibiting the reaction in the aqueous solution is more effectively exhibited.
上記ＰＶＡは、下記式（Ｉ）を満たす。
３７０≦Ｐ×Ｓ≦６，０００ ・・・（Ｉ）
Ｐ：粘度平均重合度
Ｓ：上記単量体単位の含有率（モル％）
The PVA satisfies the following formula (I).
370 ≦ P × S ≦ 6,000 (I)
P: Viscosity average degree of polymerization S: Content of the monomer unit (mol%)
上記粘度平均重合度（Ｐ）は、ＪＩＳ−Ｋ６７２６に準じて測定される。すなわち、上記ＰＶＡをけん化度が９９．５モル％未満の場合は、けん化度９９．５モル％以上に再けん化し、精製した後、３０℃の水中で測定した極限粘度［η］（単位：デシリットル／ｇ）から次式により求めることができる。
Ｐ＝（［η］×１０００／８．２９）（１／０．６２）
The viscosity average degree of polymerization (P) is measured according to JIS-K6726. That is, when the saponification degree of the PVA is less than 99.5 mol%, the saponification degree is re-saponified to 99.5 mol% or more, and after purification, the intrinsic viscosity [η] measured in water at 30 ° C. (unit: (Deciliter / g) can be obtained by the following equation.
P = ([η] × 1000 / 8.29) (1 / 0.62)
上記単量体単位の含有率（Ｓ：モル％）は、けん化する前のビニルエステル系重合体のプロトンＮＭＲから求められる。ここで、けん化する前のビニルエステル系重合体のプロトンＮＭＲを測定するに際しては、このビニルエステル系重合体をヘキサン−アセトンにより再沈精製して重合体中から未反応のシリル基を有する単量体を十分に取り除き、次いで９０℃減圧乾燥を２日間行った後、ＣＤＣｌ３溶媒に溶解して分析に供する。 The content of the monomer unit (S: mol%) can be obtained from proton NMR of the vinyl ester polymer before saponification. Here, when the proton NMR of the vinyl ester polymer before saponification is measured, the vinyl ester polymer is purified by reprecipitation with hexane-acetone, and the monomer having an unreacted silyl group is contained in the polymer. The body is sufficiently removed and then dried at 90 ° C. under reduced pressure for 2 days, and then dissolved in CDCl 3 solvent for analysis.
粘度平均重合度（Ｐ）と上記単量体単位の含有率（Ｓ）との積（Ｐ×Ｓ）は、分子１００個あたりの上記単量体単位の数（平均値）に相当する。この積（Ｐ×Ｓ）が上記下限未満の場合は、当該防曇剤から得られる塗膜の防曇性、持続的防曇性及び基材への密着性等のシリル基に由来する諸特性を十分に発揮することができない。逆に、この積（Ｐ×Ｓ）が上記上限を超えると水溶性や粘度安定性が低下する。積（Ｐ×Ｓ）は、下記式（Ｉ’）を満たすことが好ましく、下記式（Ｉ’’）を満たすことがより好ましい。
４００≦Ｐ×Ｓ≦３，０００ ・・・（Ｉ'）
５００≦Ｐ×Ｓ≦２，０００ ・・・（Ｉ’’）
The product (P × S) of the viscosity average degree of polymerization (P) and the content (S) of the monomer units corresponds to the number (average value) of the monomer units per 100 molecules. When this product (P × S) is less than the above lower limit, various properties derived from the silyl group such as antifogging property, continuous antifogging property and adhesion to a substrate of the coating film obtained from the antifogging agent. Cannot be fully utilized. On the other hand, when this product (P × S) exceeds the above upper limit, water solubility and viscosity stability decrease. The product (P × S) preferably satisfies the following formula (I ′), and more preferably satisfies the following formula (I ″).
400 ≦ P × S ≦ 3,000 (I ′)
500 ≦ P × S ≦ 2,000 (I ″)
上記ＰＶＡは、下記式（ＩＩ）及び（ＩＩＩ）をさらに満たすことが好ましい。
２００≦Ｐ≦４，０００ ・・・（ＩＩ）
０．１≦Ｓ≦１０ ・・・（ＩＩＩ）
Ｐ：粘度平均重合度
Ｓ：上記単量体単位の含有率（モル％）
The PVA preferably further satisfies the following formulas (II) and (III).
200 ≦ P ≦ 4,000 (II)
0.1 ≦ S ≦ 10 (III)
P: Viscosity average degree of polymerization S: Content of the monomer unit (mol%)
このように粘度平均重合度（Ｐ）及び上記単量体単位の含有率（Ｓ）を上記範囲とすることで、水溶性及び粘度安定性、得られる塗膜の防曇性、持続的防曇性及び基材への密着性等をより高めることができる。 Thus, by setting the viscosity average degree of polymerization (P) and the content (S) of the monomer unit in the above ranges, water solubility and viscosity stability, antifogging properties of the resulting coating film, and continuous antifogging are achieved. Property and adhesion to the substrate can be further improved.
さらには、上記粘度平均重合度（Ｐ）において、下記式（ＩＩ’）を満たすことがより好ましく、下記式（ＩＩ’’）を満たすことがさらに好ましい。
５００≦Ｐ≦３，０００ ・・・（ＩＩ’）
１，０００≦Ｐ≦２，４００ ・・・（ＩＩ’’）
Furthermore, in the viscosity average polymerization degree (P), it is more preferable to satisfy the following formula (II ′), and it is more preferable to satisfy the following formula (II ″).
500 ≦ P ≦ 3,000 (II ′)
1,000 ≦ P ≦ 2,400 (II ″)
粘度平均重合度（Ｐ）が上記下限未満の場合は、得られる塗膜の防曇性、持続的防曇性及び基材への密着性等が低下する場合がある。逆に、粘度平均重合度（Ｐ）が上記上限を超える場合は、水溶性、粘度安定性等が低下する場合がある。 When the viscosity average degree of polymerization (P) is less than the above lower limit, the anti-fogging property, continuous anti-fogging property, adhesion to the substrate, etc. of the resulting coating film may be lowered. Conversely, when the viscosity average degree of polymerization (P) exceeds the above upper limit, water solubility, viscosity stability and the like may be lowered.
また、上記単量体単位の含有率においては、下記式（ＩＩＩ’）を満たすことがより好ましく、下記式（ＩＩＩ’’）を満たすことがさらに好ましい。
０．２５≦Ｓ≦６ ・・・（ＩＩＩ’）
０．５≦Ｓ≦５ ・・・（ＩＩＩ’'）
Moreover, in the content rate of the said monomer unit, it is more preferable to satisfy | fill following formula (III '), and it is still more preferable to satisfy | fill following formula (III'').
0.25 ≦ S ≦ 6 (III ′)
0.5 ≦ S ≦ 5 (III ″)
上記単量体単位の含有率（Ｓ）が上記下限未満の場合は、得られる塗膜の防曇性、持続的防曇性及び基材への密着性等が低下する場合がある。逆に、上記単量体単位の含有率（Ｓ）が上記上限を超える場合は、水溶性や粘度安定性等が低下する場合がある。 When the content rate (S) of the monomer unit is less than the lower limit, the anti-fogging property, the continuous anti-fogging property and the adhesion to the base material of the resulting coating film may be lowered. On the other hand, when the content (S) of the monomer unit exceeds the upper limit, water solubility and viscosity stability may be deteriorated.
上記ＰＶＡのけん化度としては、特に制限はないが、８０モル％以上が好ましく、９０モル％以上がより好ましく、９５モル％以上がさらに好ましく、９７モル％以上が特に好ましい。上記ＰＶＡのけん化度が上記下限未満の場合は、得られる塗膜の防曇性、持続的防曇性及び基材への密着性等が低下する場合がある。なお、上記ＰＶＡのけん化度の上限としては、特に制限はないが、生産性等を考慮すると、例えば９９．９モル％である。ここでＰＶＡのけん化度は、ＪＩＳ−Ｋ６７２６に記載の方法に準じて測定した値をいう。 Although there is no restriction | limiting in particular as the saponification degree of the said PVA, 80 mol% or more is preferable, 90 mol% or more is more preferable, 95 mol% or more is more preferable, 97 mol% or more is especially preferable. When the degree of saponification of the PVA is less than the above lower limit, the anti-fogging property, continuous anti-fogging property, adhesion to the substrate, etc. of the resulting coating film may be lowered. The upper limit of the saponification degree of the PVA is not particularly limited, but is 99.9 mol%, for example, in consideration of productivity. Here, the degree of saponification of PVA refers to a value measured according to the method described in JIS-K6726.
＜ＰＶＡの製造方法＞
上記ＰＶＡの製造方法としては、特に限定されないが、例えば、ビニルエステル系単量体と、上記式（１）で表される基を有する単量体とを共重合させ、得られる共重合体（ビニルエステル系重合体）をけん化することにより得ることができる。
<Method for producing PVA>
Although it does not specifically limit as a manufacturing method of the said PVA, For example, a copolymer obtained by copolymerizing a vinyl ester monomer and the monomer which has group represented by the said Formula (1) ( It can be obtained by saponifying a vinyl ester polymer).
上記ビニルエステル系単量体としては、例えばギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、バレリン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、安息香酸ビニル、ピバリン酸ビニル、バーサチック酸ビニル等が挙げられる。これらの中でも、酢酸ビニルが好ましい。 Examples of the vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, vinyl versatate and the like. Can be mentioned. Among these, vinyl acetate is preferable.
また、上記式（１）で表される基を有する単量体とビニルエステル系単量体との共重合に際して、得られるＰＶＡの粘度平均重合度（Ｐ）を調節すること等を目的として、本発明の趣旨を損なわない範囲で連鎖移動剤の存在下で重合を行っても差し支えない。連鎖移動剤としては、アセトアルデヒド、プロピオンアルデヒド等のアルデヒド類；アセトン、メチルエチルケトン等のケトン類；３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルトリエトキシシラン、２−ヒドロキシエタンチオール、ｎ−ドデカンチオール、メルカプト酢酸、３−メルカプトプロピオン酸等のメルカプタン類；テトラクロロメタン、ブロモトリクロロメタン、トリクロロエチレン、パークロロエチレン等のハロゲン化炭化水素類が挙げられる。 In addition, for the purpose of adjusting the viscosity average polymerization degree (P) of the obtained PVA at the time of copolymerization of the monomer having a group represented by the above formula (1) and a vinyl ester monomer, Polymerization may be carried out in the presence of a chain transfer agent as long as the gist of the present invention is not impaired. Examples of the chain transfer agent include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-hydroxyethanethiol, n-dodecanethiol, Mercaptans such as mercaptoacetic acid and 3-mercaptopropionic acid; and halogenated hydrocarbons such as tetrachloromethane, bromotrichloromethane, trichloroethylene and perchloroethylene.
上記式（１）で表される基を有する単量体としては、例えば下記式（５）で表される化合物が挙げられる。下記式（５）で表される化合物を使用することにより、最終的に、上記式（２）で表される基を有する単量体単位を含むＰＶＡが容易に得られる。 As a monomer which has group represented by the said Formula (1), the compound represented, for example by following formula (5) is mentioned. By using a compound represented by the following formula (5), finally, a PVA containing a monomer unit having a group represented by the above formula (2) can be easily obtained.
式（５）中、Ｒ１〜Ｒ５、Ｘ、ｍ及びｎの定義は、式（２）と同様である。また、これらの好ましい基又は数値範囲も同様である。 In formula (5), the definitions of R 1 to R 5 , X, m, and n are the same as in formula (2). The same applies to these preferred groups or numerical ranges.
上記式（５）で表される化合物としては、例えば３−（メタ）アクリルアミドプロピルトリメトキシシラン、４−（メタ）アクリルアミドブチルトリメトキシシラン、６−（メタ）アクリルアミドヘキシルトリメトキシシラン、８−（メタ）アクリルアミドオクチルトリメトキシシラン、１２−（メタ）アクリルアミドドデシルトリメトキシシラン、１８−（メタ）アクリルアミドオクタデシルトリメトキシシラン、３−（メタ）アクリルアミドプロピルトリエトキシシラン、３−（メタ）アクリルアミドプロピルトリブトキシシラン、３−（メタ）アクリルアミドプロピルメチルジメトキシシラン、３−（メタ）アクリルアミドプロピルジメチルメトキシシラン、３−（メタ）アクリルアミド−３−メチルブチルトリメトキシシラン、４−（メタ）アクリルアミド−４−メチルブチルトリメトキシシラン、４−（メタ）アクリルアミド−３−メチルブチルトリメトキシシラン、５−（メタ）アクリルアミド−５−メチルヘキシルトリメトキシシラン、４−ペンテニルトリメトキシシラン、５−へキセニルトリメトキシシラン等が挙げられる。 Examples of the compound represented by the above formula (5) include 3- (meth) acrylamidopropyltrimethoxysilane, 4- (meth) acrylamidobutyltrimethoxysilane, 6- (meth) acrylamidehexyltrimethoxysilane, 8- ( (Meth) acrylamide octyltrimethoxysilane, 12- (meth) acrylamide dodecyltrimethoxysilane, 18- (meth) acrylamide octadecyltrimethoxysilane, 3- (meth) acrylamidepropyltriethoxysilane, 3- (meth) acrylamidepropyltributoxy Silane, 3- (meth) acrylamidopropylmethyldimethoxysilane, 3- (meth) acrylamidopropyldimethylmethoxysilane, 3- (meth) acrylamide-3-methylbutyltrimethoxysilane, 4- (Meth) acrylamide-4-methylbutyltrimethoxysilane, 4- (meth) acrylamide-3-methylbutyltrimethoxysilane, 5- (meth) acrylamide-5-methylhexyltrimethoxysilane, 4-pentenyltrimethoxysilane, 5 -Hexenyltrimethoxysilane and the like.
上記ビニルエステル系単量体と上記式（１）で表される基を有する単量体とを共重合させる方法としては、塊状重合法、溶液重合法、懸濁重合法、乳化重合法等の公知の方法が挙げられる。特に、重合温度が３０℃より低い場合には、乳化重合法が好ましく、重合温度が３０℃以上の場合には、無溶媒で行う塊状重合法又はアルコール等の溶媒を用いて行う溶液重合法が通常採用される。 Examples of the method for copolymerizing the vinyl ester monomer and the monomer having the group represented by the formula (1) include a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. A well-known method is mentioned. In particular, when the polymerization temperature is lower than 30 ° C., an emulsion polymerization method is preferable, and when the polymerization temperature is 30 ° C. or higher, a bulk polymerization method performed without solvent or a solution polymerization method performed using a solvent such as alcohol is used. Usually adopted.
乳化重合法の場合、溶媒としては水が挙げられ、メタノール、エタノール等の低級アルコールを併用してもよい。また、乳化剤としては、公知の乳化剤を使用することができる。共重合の際の開始剤としては、鉄イオン−酸化剤−還元剤を併用したレドックス系開始剤が重合をコントロールする上で好適に用いられる。塊状重合法や溶液重合法の場合、共重合反応を行うにあたって、反応の方式は回分式及び連続式のいずれの方式にても実施可能である。溶液重合法を採用して共重合反応を行う際に、溶媒として使用されるアルコールとしては、メタノール、エタノール、プロパノール等の低級アルコールが挙げられる。この場合の共重合反応に使用される開始剤としては、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）、２，２’−アゾビス（Ｎ−ブチル−２−メチルプロピオンアミド）などのアゾ系開始剤；過酸化ベンゾイル、ｎ−プロピルパーオキシカーボネートなどの過酸化物系開始剤などの公知の開始剤が挙げられる。共重合反応を行う際の重合温度については特に制限はないが、５℃〜５０℃の範囲が適当である。 In the case of the emulsion polymerization method, examples of the solvent include water, and lower alcohols such as methanol and ethanol may be used in combination. Moreover, a well-known emulsifier can be used as an emulsifier. As an initiator for copolymerization, a redox initiator using iron ions, an oxidizing agent and a reducing agent in combination is preferably used for controlling the polymerization. In the case of the bulk polymerization method or the solution polymerization method, the reaction can be carried out by either a batch method or a continuous method in carrying out the copolymerization reaction. When the copolymerization reaction is carried out using the solution polymerization method, examples of the alcohol used as the solvent include lower alcohols such as methanol, ethanol, and propanol. Examples of the initiator used for the copolymerization reaction in this case include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis ( Azo initiators such as cyclohexane-1-carbonitrile) and 2,2′-azobis (N-butyl-2-methylpropionamide); peroxide initiators such as benzoyl peroxide and n-propyl peroxycarbonate And known initiators such as Although there is no restriction | limiting in particular about the polymerization temperature at the time of performing a copolymerization reaction, The range of 5 to 50 degreeC is suitable.
この共重合反応の際には、本発明の趣旨が損なわれない範囲であれば、必要に応じて、共重合可能な単量体を共重合させることができる。このような単量体としては、エチレン、プロピレン、１−ブテン、イソブテン、１−ヘキセン等のα−オレフィン類；フマール酸、マレイン酸、イタコン酸、無水マレイン酸、無水イタコン酸等のカルボン酸又はその誘導体；アクリル酸又はその塩、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸イソプロピル等のアクリル酸エステル類；メタクリル酸又はその塩、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−プロピル、メタクリル酸イソプロピル等のメタクリル酸エステル類；アクリルアミド、Ｎ−メチルアクリルアミド、Ｎ−エチルアクリルアミド等のアクリルアミド誘導体；メタクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ−エチルメタクリルアミド等のメタクリルアミド誘導体；メチルビニルエーテル、エチルビニルエーテル、ｎ−プロピルビニルエーテル、イソプロピルビニルエーテル、ｎ−ブチルビニルエーテル等のビニルエーテル類；エチレングリコールビニルエーテル、１，３−プロパンジオールビニルエーテル、１，４−ブタンジオールビニルエーテル等のヒドロキシ基含有ビニルエーテル類；アリルアセテート；プロピルアリルエーテル、ブチルアリルエーテル、ヘキシルアリルエーテル等のアリルエーテル類；オキシアルキレン基を有する単量体；酢酸イソプロペニル；３−ブテン−１−オール、４−ペンテン−１−オール、５−ヘキセン−１−オール、７−オクテン−１−オール、９−デセン−１−オール、３−メチル−３−ブテン−１−オール等のヒドロキシ基含有α−オレフィン類；ビニルスルホン酸、アリルスルホン酸、メタアリルスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸等のスルホン酸基を有する単量体；ビニロキシエチルトリメチルアンモニウムクロライド、ビニロキシブチルトリメチルアンモニウムクロライド、ビニロキシエチルジメチルアミン、ビニロキシメチルジエチルアミン、Ｎ−アクリルアミドメチルトリメチルアンモニウムクロライド、Ｎ−アクリルアミドエチルトリメチルアンモニウムクロライド、Ｎ−アクリルアミドジメチルアミン、アリルトリメチルアンモニウムクロライド、メタアリルトリメチルアンモニウムクロライド、ジメチルアリルアミン、アリルエチルアミン等のカチオン基を有する単量体などが挙げられる。これらの単量体の使用量は、その使用される目的や用途等によっても異なるが、通常、共重合に用いられる全ての単量体を基準にした割合で２０モル％以下であり、１０モル％以下であることが好ましい。 In the case of this copolymerization reaction, a copolymerizable monomer can be copolymerized as necessary as long as the gist of the present invention is not impaired. Examples of such a monomer include α-olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene; carboxylic acids such as fumaric acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride; Derivatives thereof; acrylic acid or salts thereof, acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate; methacrylic acid or salts thereof, methyl methacrylate, ethyl methacrylate, n methacrylate -Methacrylic acid esters such as propyl and isopropyl methacrylate; Acrylamide derivatives such as acrylamide, N-methylacrylamide and N-ethylacrylamide; Methacrylamide derivatives such as methacrylamide, N-methylmethacrylamide and N-ethylmethacrylamide; Vinyl ethers such as til vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether; hydroxy group-containing vinyl ethers such as ethylene glycol vinyl ether, 1,3-propanediol vinyl ether, 1,4-butanediol vinyl ether; Allyl ethers; allyl ethers such as propyl allyl ether, butyl allyl ether, hexyl allyl ether; monomers having an oxyalkylene group; isopropenyl acetate; 3-buten-1-ol, 4-penten-1-ol, 5 -Hydroxyl-containing α-olefins such as hexen-1-ol, 7-octen-1-ol, 9-decen-1-ol, 3-methyl-3-buten-1-ol; vinyl sulfone , Monomers having a sulfonic acid group such as allylsulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid; vinyloxyethyltrimethylammonium chloride, vinyloxybutyltrimethylammonium chloride, vinyloxyethyldimethylamine , Having a cationic group such as vinyloxymethyldiethylamine, N-acrylamidomethyltrimethylammonium chloride, N-acrylamidoethyltrimethylammonium chloride, N-acrylamidodimethylamine, allyltrimethylammonium chloride, methallyltrimethylammonium chloride, dimethylallylamine, allylethylamine And monomers. The amount of these monomers used varies depending on the purpose and application of use, but is usually 20 mol% or less based on all monomers used for copolymerization, % Or less is preferable.
上記共重合により得られたビニルエステル系重合体は、次いで、公知の方法に従って溶媒中でけん化され、ＰＶＡへと導かれる。 The vinyl ester polymer obtained by the copolymerization is then saponified in a solvent according to a known method and led to PVA.
けん化反応の触媒としては、通常、アルカリ性物質が用いられ、その例として、水酸化カリウム、水酸化ナトリウム等のアルカリ金属の水酸化物、及びナトリウムメトキシド等のアルカリ金属アルコキシド等が挙げられる。上記アルカリ性物質の使用量は、ビニルエステル系重合体中のビニルエステル系単量体単位を基準にしたモル比で、０．００４〜０．５の範囲内であることが好ましく、０．００５〜０．０５の範囲内であることがより好ましい。また、この触媒は、けん化反応の初期に一括して添加してもよいし、けん化反応の初期に一部を添加し、残りをけん化反応の途中で追加して添加してもよい。 As the catalyst for the saponification reaction, an alkaline substance is usually used, and examples thereof include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and alkali metal alkoxides such as sodium methoxide. The amount of the alkaline substance used is preferably in the range of 0.004 to 0.5 in terms of a molar ratio based on the vinyl ester monomer unit in the vinyl ester polymer. More preferably, it is in the range of 0.05. Further, this catalyst may be added all at once in the early stage of the saponification reaction, or a part thereof may be added in the early stage of the saponification reaction, and the rest may be added in the middle of the saponification reaction.
けん化反応に用いることができる溶媒としては、例えばメタノール、酢酸メチル、ジメチルスルホキシド、ジエチルスルホキシド、ジメチルホルムアミド等が挙げられる。これらの溶媒の中でもメタノールが好ましい。また、メタノールの使用にあたり、メタノール中の含水率が好ましくは０．００１〜１質量％、より好ましくは０．００３〜０．９質量％、特に好ましくは０．００５〜０．８質量％に調整されているのがよい。 Examples of the solvent that can be used for the saponification reaction include methanol, methyl acetate, dimethyl sulfoxide, diethyl sulfoxide, dimethylformamide, and the like. Of these solvents, methanol is preferred. Further, in the use of methanol, the water content in methanol is preferably adjusted to 0.001 to 1% by mass, more preferably 0.003 to 0.9% by mass, and particularly preferably 0.005 to 0.8% by mass. It is good to be.
けん化反応は、好ましくは５℃〜８０℃、より好ましくは２０℃〜７０℃の温度で行われる。けん化反応に必要とされる時間としては、好ましくは５分間〜１０時間、より好ましくは１０分間〜５時間である。けん化反応は、バッチ法及び連続法のいずれの方式にても実施可能である。けん化反応の終了後に、必要に応じて、残存するけん化触媒を中和してもよく、使用可能な中和剤として、酢酸、乳酸などの有機酸、及び酢酸メチル等のエステル化合物等が挙げられる。 The saponification reaction is preferably performed at a temperature of 5 ° C to 80 ° C, more preferably 20 ° C to 70 ° C. The time required for the saponification reaction is preferably 5 minutes to 10 hours, more preferably 10 minutes to 5 hours. The saponification reaction can be carried out by either a batch method or a continuous method. After completion of the saponification reaction, the remaining saponification catalyst may be neutralized as necessary, and usable neutralizing agents include organic acids such as acetic acid and lactic acid, and ester compounds such as methyl acetate. .
けん化反応により得られたＰＶＡは、必要に応じて、洗浄することができる。この洗浄の際に用いられる洗浄液としては、メタノール等の低級アルコール、酢酸メチル等の低級脂肪酸エステル、及びそれらの混合物等が挙げられる。これらの洗浄液には、少量の水やアルカリ又は酸等が添加されていてもよい。 The PVA obtained by the saponification reaction can be washed as necessary. Examples of the cleaning liquid used in this cleaning include lower alcohols such as methanol, lower fatty acid esters such as methyl acetate, and mixtures thereof. A small amount of water, alkali, acid, or the like may be added to these cleaning liquids.
当該防曇剤における上記ＰＶＡの含有割合としては、特に限定されないが、４質量％以上２０質量％以下が好ましい。当該防曇剤によれば、このように比較的高濃度とすることができるため、得られる塗膜の防曇性、持続的防曇性及び基材への密着性等を効果的に高めることができる。 Although it does not specifically limit as a content rate of the said PVA in the said antifogging agent, 4 mass% or more and 20 mass% or less are preferable. According to the anti-fogging agent, since it can be made relatively high in this way, the anti-fogging property, continuous anti-fogging property and adhesion to the base material of the obtained coating film are effectively enhanced. Can do.
＜無機物＞
当該防曇剤は、無機物をさらに含有することが好ましい。これにより、得られる塗膜の耐水性を向上させることができ、その結果、塗膜の防曇性、持続的防曇性及び基材への密着性をさらに高めることができる。無機物としては、アルミニウム、ケイ素、マグネシウム、カルシウム等の元素を含むものが挙げられ、具体的には、クレー、タルク、炭酸カルシウム、ケイ酸カルシウム、シリカ、酸化アルミニウム等が挙げられる。また、水ガラス、水溶性アルミニウム化合物、炭酸ジルコニウムアンモニウム等の水溶性無機物も使用し得る。しかしながら、水溶液無機物を高濃度で使用する場合には、得られる防曇剤の粘度安定性が低くなり、場合によってはゲルを発生するおそれがあるので、必ずしも好ましくない。したがって、本発明の効果をより高めるためには水不溶性の無機物の微粒子を使用することが好ましく、粒子径が２００ｎｍ以下の微粒子がより好ましく、粒子径１００ｎｍ以下の微粒子がさらに好ましい。粒子径が２００ｎｍを超える場合には、塗膜の透明性が悪化するおそれがある。特に好適なものとしては、コロイダルシリカあるいはコロイダルアルミナが挙げられ、コロイダルシリカが最適である。コロイダルシリカを使用した場合には、塗膜の透明性および吸水時の表面硬度が良好になる。
<Inorganic material>
The antifogging agent preferably further contains an inorganic substance. Thereby, the water resistance of the coating film obtained can be improved, and as a result, the antifogging property, the continuous antifogging property of the coating film, and the adhesiveness to a base material can further be improved. Examples of the inorganic substance include those containing elements such as aluminum, silicon, magnesium, and calcium, and specific examples include clay, talc, calcium carbonate, calcium silicate, silica, and aluminum oxide. Water-soluble inorganic substances such as water glass, water-soluble aluminum compounds, and ammonium zirconium carbonate can also be used. However, when an aqueous inorganic substance is used at a high concentration, the viscosity stability of the resulting antifogging agent is lowered, and in some cases, a gel may be generated. Therefore, in order to further enhance the effect of the present invention, it is preferable to use water-insoluble inorganic fine particles, more preferably fine particles having a particle size of 200 nm or less, and even more preferably fine particles having a particle size of 100 nm or less. When the particle diameter exceeds 200 nm, the transparency of the coating film may be deteriorated. Particularly preferred is colloidal silica or colloidal alumina, and colloidal silica is most suitable. When colloidal silica is used, the transparency of the coating film and the surface hardness during water absorption are improved.
当該防曇剤において、ビニルアルコール系重合体と無機物との質量比［（ビニルアルコール系重合体）／（無機物）］は、０．１／９９．９〜１００／０が好ましく、１／９９〜９５／５がより好ましく、１０／９０〜９０／１０がさらに好ましく、２５／７５〜７５／２５が特に好ましい。無機物の配合比率が少なすぎる場合には、吸水時の表面硬度が低くなる場合がある。一方、無機物の配合比率が多すぎる場合には、得られる塗膜の基材への密着性および乾燥時の耐擦傷性が低下する場合がある。 In the antifogging agent, the mass ratio [(vinyl alcohol polymer) / (inorganic)] between the vinyl alcohol polymer and the inorganic material is preferably 0.1 / 99.9 to 100/0, and 1/99 to 95/5 is more preferable, 10/90 to 90/10 is more preferable, and 25/75 to 75/25 is particularly preferable. If the inorganic compounding ratio is too small, the surface hardness at the time of water absorption may be low. On the other hand, when there are too many compounding ratios of an inorganic substance, the adhesiveness to the base material of the coating film obtained and the abrasion resistance at the time of drying may fall.
＜その他の成分等＞
当該防曇剤は、通常、上記ＰＶＡの水溶液である。但し、他の溶媒を用いた溶液であってもよい。当該防曇剤は、その他、
エタノール等のアルコール、ジエチルエーテル等のエーテルなどの他の溶媒；
水酸化ナトリウム、アンモニア等のアルカリ；
塩酸、酢酸等の酸；
アルブミン、ゼラチン、カゼイン、澱粉、カチオン化澱粉、アラビアゴム、ポリアミド樹脂、メラミン樹脂、ポリ（メタ）アクリルアミド、ポリビニルピロリドン、ポリ（メタ）アクリル酸ナトリウム、アニオン変性ＰＶＡ、アルギン酸ナトリウム、水溶性ポリエステル、並びにメチルセルロース、ヒドロキシエチルセルロース、及びカルボキシメチルセルロース（ＣＭＣ）などのセルロース誘導体等の水溶性樹脂；
ＳＢＲ、ＮＢＲ、エチレン−酢酸ビニル共重合体等の酢酸ビニル系樹脂、（メタ）アクリル酸エステル系樹脂、塩化ビニル系樹脂等の水分散性樹脂；
グリオキザール、グルタルアルデヒド等のアルデヒド化合物、乳酸チタン等のチタン系化合物、ポリアミドアミンエピクロルヒドリン等のエポキシ化合物、ポリオキサゾリン等の架橋剤；
γ−アミノプロピルトリエトキシシラン、ビニルトリ（β−メトキシ−エトキシ）シラン等のカップリング剤；
脂肪酸アミド型界面活性剤、カチオン界面活性剤、アニオン界面活性剤あるいはノニオン界面活性剤等の平滑剤；
水、メタノール、アセトン等の希釈剤；
無変性のＰＶＡ等の水溶性ポリマー；
等を含有してもよい。
<Other ingredients>
The antifogging agent is usually an aqueous solution of the above PVA. However, it may be a solution using another solvent. The anti-fogging agent includes other
Other solvents such as alcohols such as ethanol, ethers such as diethyl ether;
Alkali such as sodium hydroxide and ammonia;
Acids such as hydrochloric acid and acetic acid;
Albumin, gelatin, casein, starch, cationized starch, gum arabic, polyamide resin, melamine resin, poly (meth) acrylamide, polyvinylpyrrolidone, poly (meth) acrylate sodium, anion-modified PVA, sodium alginate, water-soluble polyester, and Water-soluble resins such as cellulose derivatives such as methylcellulose, hydroxyethylcellulose, and carboxymethylcellulose (CMC);
Water-dispersible resins such as SBR, NBR, vinyl acetate resins such as ethylene-vinyl acetate copolymer, (meth) acrylic acid ester resins, vinyl chloride resins;
Aldehyde compounds such as glioxal and glutaraldehyde, titanium compounds such as titanium lactate, epoxy compounds such as polyamidoamine epichlorohydrin, and cross-linking agents such as polyoxazoline;
coupling agents such as γ-aminopropyltriethoxysilane, vinyltri (β-methoxy-ethoxy) silane;
Smoothing agents such as fatty acid amide type surfactants, cationic surfactants, anionic surfactants or nonionic surfactants;
Diluents such as water, methanol, acetone;
A water-soluble polymer such as unmodified PVA;
Etc. may be contained.
＜透明部材＞
本発明の透明部材は、当該防曇剤を用いて積層される防曇層を有するため、防曇性及び持続的防曇性に優れる。当該防曇剤が塗布される基材は特に限定されず、ガラス、プラスチック、金属等が挙げられるが、透明基材であることが好ましい。本発明の透明部材は、具体的には、例えば自動車、電車、ビル等の窓ガラス、眼鏡用レンズ、浴室などの鏡、農業ハウス用プラスチックフィルム、窓ガラス用プラスチックフィルムなどの用途に好適に用いられる。
<Transparent material>
Since the transparent member of the present invention has an anti-fogging layer laminated using the anti-fogging agent, it is excellent in anti-fogging properties and continuous anti-fogging properties. The base material to which the antifogging agent is applied is not particularly limited, and examples thereof include glass, plastic, and metal, and a transparent base material is preferable. Specifically, the transparent member of the present invention is suitably used for applications such as window glass for automobiles, trains, buildings, lenses for glasses, mirrors for bathrooms, plastic films for agricultural houses, plastic films for window glasses, and the like. It is done.
本発明の防曇剤を基材表面に塗布する方法としては、例えばハケ塗り、浸漬塗り、スピンコーティング、流し塗り、スプレー塗布、ロール塗装、エアーナイフコーティング、ブレードコーティング等の通常知られている各種の方法を用いることが可能である。上記塗布後、加熱処理を適宜施すことにより、基材への密着力がより高い塗膜を得ることができる。塗膜の厚みは特に限定されないが、通常０．１μｍ〜５０μｍであり、０．２μｍ〜２０μｍが好ましい。 As a method for applying the antifogging agent of the present invention to the substrate surface, various commonly known methods such as brush coating, dip coating, spin coating, flow coating, spray coating, roll coating, air knife coating, blade coating, etc. It is possible to use this method. A coating film with higher adhesion to the substrate can be obtained by appropriately performing a heat treatment after the application. Although the thickness of a coating film is not specifically limited, Usually, they are 0.1 micrometer-50 micrometers, and 0.2 micrometer-20 micrometers are preferable.
以下、本発明を実施例により、さらに詳細に説明する。以下の実施例及び比較例において、特に断りがない場合、部及び％はそれぞれ質量部及び質量％を示す。 Hereinafter, the present invention will be described in more detail with reference to examples. In the following examples and comparative examples, unless otherwise specified, parts and% represent parts by mass and mass%, respectively.
なお、実施例及び比較例で用いたシリル基を有する単量体（モノマーＡ）は、以下のとおりである。
ＭＡｍＰＴＭＳ ：３−メタクリルアミドプロピルトリメトキシシラン
ＭＡｍＰＴＥＳ ：３−メタクリルアミドプロピルトリエトキシシラン
ＭＡｍＢＴＭＳ ：４−メタクリルアミドブチルトリメトキシシラン
ＭＡｍＯＴＭＳ ：８−メタクリルアミドオクチルトリメトキシシラン
ＭＡｍＤＤＴＭＳ：１２−メタクリルアミドドデシルトリメトキシシラン
ＭＡｍＯＤＴＭＳ：１８−メタクリルアミドオクタデシルトリメトキシシラン
ＡＭＢＴＭＳ ：３−アクリルアミド−３−メチルブチルトリメトキシシラン
４−ＰＴＭＳ ：４−ペンテニルトリメトキシシラン
ＶＭＳ ：ビニルトリメトキシシラン
ＭＡｍＭＴＭＳ ：メタクリルアミドメチルトリメトキシシラン
ＡＭＰＴＭＳ ：２−アクリルアミド−２−メチルプロピルトリメトキシシラン
In addition, the monomer (monomer A) which has the silyl group used by the Example and the comparative example is as follows.
MAmPTMS: 3-methacrylamideamidopropyltrimethoxysilane MAmPTES: 3-methacrylamideamidopropyltriethoxysilane MAmBTMS: 4-methacrylamidobutyltrimethoxysilane MAmOTMS: 8-methacrylamidooctyltrimethoxysilane MAmDDTMS: 12-methacrylamidododecyltrimethoxysilane MAmODTMS: 18-methacrylamidooctadecyltrimethoxysilane AMBTMS: 3-acrylamido-3-methylbutyltrimethoxysilane 4-PTMS: 4-pentenyltrimethoxysilane VMS: vinyltrimethoxysilane MAMTMTS: methacrylamidomethyltrimethoxysilane AMPTMS: 2 -Acrylamide-2-methylpropyltrimethoxysilane
［シリル基含有ＰＶＡの合成］
下記の方法によりＰＶＡを製造し、そのけん化度、上記式（１）で表される基を有する単量体単位の含有率（Ｓ）（一部の例では、シリル基を有する単量体単位の含有率）、粘度平均重合度（Ｐ）を求めた。また、以下の評価方法にしたがって、防曇剤の性能を評価した。
[Synthesis of silyl group-containing PVA]
PVA is produced by the following method, the degree of saponification, the content of monomer units having a group represented by the above formula (1) (S) (in some examples, monomer units having a silyl group) Content) and viscosity average degree of polymerization (P). Further, the performance of the antifogging agent was evaluated according to the following evaluation method.
［ＰＶＡの分析方法］
ＰＶＡの分析は、特に断らない限りＪＩＳ−Ｋ６７２６に記載の方法に従って行った。
[Analysis method of PVA]
Analysis of PVA was performed according to the method described in JIS-K6726 unless otherwise specified.
［合成例１］ＰＶＡ１の製造
撹拌機、還流冷却管、窒素導入管、コモノマー滴下口及び開始剤の添加口を備えた６Ｌセパラブルフラスコに、酢酸ビニル１，５００ｇ、メタノール５００ｇ、上記式（１）で表される基を有する単量体（モノマーＡ）としてのＭＡｍＰＴＭＳ１．８７ｇを仕込み、窒素バブリングをしながら３０分間系内を窒素置換した。また、ディレー溶液としてＭＡｍＰＴＭＳをメタノールに溶解して濃度８％としたコモノマー溶液を調製し、窒素ガスのバブリングにより窒素置換した。反応器の昇温を開始し、内温が６０℃となったところで、２，２’−アゾビスイソブチロニトリル（ＡＩＢＮ）０．８ｇを添加し重合を開始した。ディレー溶液を滴下して重合溶液中のモノマー組成（酢酸ビニルとモノマーＡ（ＭＡｍＰＴＭＳ）の比率）が一定となるようにしながら、６０℃で２．７時間重合した後、冷却して重合を停止した。重合を停止するまで加えたコモノマー溶液（逐次添加液）の総量は９９ｇであった。また、重合停止時の固形分濃度は２９．０％であった。続いて３０℃、減圧下でメタノールを時々添加しながら未反応の酢酸ビニルモノマーの除去を行い、上記式（１）で表される基を有するポリ酢酸ビニル（ＰＶＡｃ）を４０％含有するメタノール溶液を得た。さらに、これにＰＶＡｃ中の酢酸ビニル単位に対する水酸化ナトリウムのモル比が０．０４、ＰＶＡｃの固形分濃度が３０質量％となるように、メタノール及び水酸化ナトリウムを１０質量％含有するメタノール溶液をこの順序で撹拌下に加え、４０℃でけん化反応を開始した。アルカリ溶液を添加後、約５分でゲル状物が生成した。このゲル状物を粉砕器にて粉砕し、４０℃で１時間放置してけん化を進行させた後、酢酸メチルを加えて残存するアルカリを中和した。フェノールフタレイン指示薬を用いて中和が終了したことを確認した後、濾別して白色固体を得、これにメタノールを加えて室温で３時間放置洗浄した。上記の洗浄操作を３回繰り返した後、遠心脱液して得られた白色固体を乾燥機中６５℃で２日間放置し、上記式（１）で表される基を有するＰＶＡ１を得た。ＰＶＡ１の粘度平均重合度（Ｐ）は１，７００、けん化度は９８．６モル％であった。
[Synthesis Example 1] Production of PVA1 Into a 6 L separable flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a comonomer dropping port and an initiator addition port, 1,500 g of vinyl acetate, 500 g of methanol, the above formula (1 ) MAmPTMS 1.87 g as a monomer (monomer A) having a group represented by) was charged, and the inside of the system was purged with nitrogen for 30 minutes while carrying out nitrogen bubbling. Further, a comonomer solution having a concentration of 8% was prepared by dissolving MAmPTMS in methanol as a delay solution, and nitrogen substitution was performed by bubbling nitrogen gas. The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.8 g of 2,2′-azobisisobutyronitrile (AIBN) was added to initiate polymerization. The delay solution was added dropwise to polymerize the monomer composition (ratio of vinyl acetate and monomer A (MAmPTMS)) in the polymerization solution at a constant rate for 2.7 hours at 60 ° C. and then cooled to stop the polymerization. . The total amount of comonomer solution (sequentially added solution) added until the polymerization was stopped was 99 g. Further, the solid content concentration when the polymerization was stopped was 29.0%. Subsequently, an unreacted vinyl acetate monomer is removed while sometimes adding methanol under reduced pressure at 30 ° C., and a methanol solution containing 40% of polyvinyl acetate (PVAc) having a group represented by the above formula (1) Got. Furthermore, a methanol solution containing 10% by mass of methanol and sodium hydroxide was added so that the molar ratio of sodium hydroxide to the vinyl acetate unit in PVAc was 0.04 and the solid content concentration of PVAc was 30% by mass. In this order, with stirring, the saponification reaction was started at 40 ° C. A gel was formed in about 5 minutes after the addition of the alkaline solution. This gel-like material was pulverized with a pulverizer and allowed to stand at 40 ° C. for 1 hour to allow saponification to proceed. Then, methyl acetate was added to neutralize the remaining alkali. After confirming the completion of neutralization using a phenolphthalein indicator, the mixture was filtered to obtain a white solid. Methanol was added thereto, and the mixture was allowed to wash at room temperature for 3 hours. After repeating the above washing operation three times, the white solid obtained by centrifugal drainage was left in a dryer at 65 ° C. for 2 days to obtain PVA1 having a group represented by the above formula (1). PVA1 had a viscosity average polymerization degree (P) of 1,700 and a saponification degree of 98.6 mol%.
得られたＰＶＡ１の上記式（１）で表される基を有する単量体単位の含有率（シリル基を有する単量体単位の含有率）は、このＰＶＡの前駆体であるＰＶＡｃのプロトンＮＭＲから求めた。具体的には、得られたＰＶＡｃの再沈精製をｎ−ヘキサン／アセトンで３回以上十分に行った後、５０℃の減圧下で乾燥を２日間行い、分析用のＰＶＡｃを作製した。このＰＶＡｃをＣＤＣｌ３に溶解させ、５００ＭＨｚのプロトンＮＭＲ（ＪＥＯＬ ＧＸ−５００）を用いて室温で測定した。酢酸ビニル単位の主鎖メチンに由来するピークα（４．７〜５．２ｐｐｍ）とモノマーＡ単位のメトキシ基のメチルに由来するピークβ（３．４〜３．８ｐｐｍ）とから、下記式を用いて式（１）で表される基を有する単量体単位の含有率（Ｓ）を算出した。ＰＶＡ１において、含有率（Ｓ）は０．５モル％であった。得られたＰＶＡについて分析した結果を表１に示す。
式（１）で表される基を有する単量体単位の含有率（Ｓ：モル％）
＝｛（βのピーク面積／９）／（αのピーク面積＋（βのピーク面積／９））｝×１００
The content of the monomer unit having the group represented by the above formula (1) of the obtained PVA1 (content of the monomer unit having a silyl group) is the proton NMR of PVAc which is a precursor of this PVA. I asked for it. Specifically, after reprecipitation purification of the obtained PVAc was sufficiently performed three times or more with n-hexane / acetone, drying was performed under reduced pressure at 50 ° C. for 2 days to prepare a PVAc for analysis. This PVAc was dissolved in CDCl 3 and measured at room temperature using 500 MHz proton NMR (JEOL GX-500). From the peak α (4.7 to 5.2 ppm) derived from the main chain methine of the vinyl acetate unit and the peak β (3.4 to 3.8 ppm) derived from the methyl of the methoxy group of the monomer A unit, the following formula is obtained. The content (S) of the monomer unit having a group represented by the formula (1) was calculated. In PVA1, the content (S) was 0.5 mol%. The results of analyzing the obtained PVA are shown in Table 1.
Content of monomer unit having group represented by formula (1) (S: mol%)
= {(Peak area of β / 9) / (peak area of α + (peak area of β / 9))} × 100
［合成例２〜２１及び比較合成例１〜１５］ＰＶＡ２〜ＰＶＡ３６の製造
酢酸ビニル及びメタノールの仕込み量、モノマーＡの種類や添加量等の重合条件、けん化時におけるＰＶＡｃの濃度、酢酸ビニル単位に対する水酸化ナトリウムのモル比等のけん化条件を表１に示すように変更したこと以外は、合成例１と同様にしてＰＶＡ２〜ＰＶＡ３６を得た。得られた各ＰＶＡについて分析した結果を表１に示す。
なお、表１中、比較合成例１〜１５の含有率（Ｓ）は、式（１）で表される基を有する単量体単位以外の、シリル基を有する単量体単位の含有率も含む。
[Synthesis Examples 2 to 21 and Comparative Synthesis Examples 1 to 15] Manufacture of PVA2 to PVA36 Polymerization conditions such as the amount of vinyl acetate and methanol, the type and addition amount of monomer A, the concentration of PVAc during saponification, and the vinyl acetate unit PVA2 to PVA36 were obtained in the same manner as in Synthesis Example 1 except that the saponification conditions such as the molar ratio of sodium hydroxide were changed as shown in Table 1. Table 1 shows the results of analysis for each obtained PVA.
In Table 1, the content (S) of Comparative Synthesis Examples 1 to 15 is the content of monomer units having a silyl group other than the monomer unit having a group represented by Formula (1). Including.
［実施例１］
＜防曇剤の製造と評価＞
ＰＶＡ１の１０％水溶液を調製し、この水溶液１００部にコロイダルシリカ「スノーテックス２０」（日産化学工業製、粒子径１０〜２０ｎｍ、固形分２０質量％）を２０部加えて防曇剤を得た。この防曇剤を、下記の評価方法にしたがって、ガラス板に塗布し、塗膜の防曇性、塗膜の持続的防曇性および塗膜のガラスへの密着性を評価した。また、防曇剤の粘度安定性も評価した。結果を表２に示す。なお、表２中、※１は、ＰＶＡが水溶液に対して完全に溶解しないため、評価できなかったことを示す。
[Example 1]
<Manufacture and evaluation of anti-fogging agent>
A 10% aqueous solution of PVA1 was prepared, and 20 parts of colloidal silica “Snowtex 20” (manufactured by Nissan Chemical Industries, particle size 10-20 nm, solid content 20 mass%) was added to 100 parts of this aqueous solution to obtain an antifogging agent. . This antifogging agent was applied to a glass plate according to the following evaluation method, and the antifogging property of the coating film, the continuous antifogging property of the coating film, and the adhesion of the coating film to glass were evaluated. The viscosity stability of the antifogging agent was also evaluated. The results are shown in Table 2. In Table 2, * 1 indicates that PVA could not be evaluated because it was not completely dissolved in the aqueous solution.
［塗膜の防曇性］
上記調製した防曇剤を５ｍｍ厚のガラス板上に、乾燥後の塗膜厚みが２μｍになるようにメイヤーバーでコートし、７０℃で１分間乾燥してコートガラス板を得た。４０℃の温水１００ｍＬを入れた２００ｍＬビーカーの口を上記コートガラス板で覆い、４０℃雰囲気中、２４時間放置した後、コート面の水滴の付着具合を目視で観察し、以下の基準にしたがって判定した。結果を表２に示す。
Ａ：水がコート面全体に一様に付着し、曇りは認められなかった
Ｂ：コート面全体の１０％程度に曇りが認められた
Ｃ：コート面全体の３０％程度に曇りが認められた
Ｄ：水滴が付着しており、著しい曇りが認められた
Ｅ：塗膜が溶解した
[Anti-fogging property of coating film]
The prepared antifogging agent was coated on a 5 mm thick glass plate with a Mayer bar so that the thickness of the dried coating film was 2 μm, and dried at 70 ° C. for 1 minute to obtain a coated glass plate. Cover the mouth of a 200 mL beaker containing 100 mL of 40 ° C. warm water with the above coated glass plate, leave it in a 40 ° C. atmosphere for 24 hours, and then visually observe the degree of water droplet adhesion on the coated surface, and determine according to the following criteria: did. The results are shown in Table 2.
A: Water uniformly adhered to the entire coated surface, and no cloudiness was observed. B: Cloudiness was observed in about 10% of the entire coated surface. C: Cloudiness was observed in about 30% of the entire coated surface. D: Water droplets adhered and significant clouding was observed E: Coating film dissolved
［塗膜の持続的防曇性］
上記調製した防曇剤を５ｍｍ厚のガラス板上に、乾燥後の塗膜厚みが２μｍになるようにメイヤーバーでコートし、７０℃で１分間乾燥してコートガラス板を得た。このコートガラス板を４０℃の水に１週間浸漬した後、７０℃で１分間乾燥した。４０℃の温水１００ｍＬを入れた２００ｍＬビーカーの口を上記処理を行ったコートガラス板で覆い、４０℃雰囲気中、２４時間放置した後、コート面の水滴の付着具合を目視で観察し、以下の基準にしたがって判定した。結果を表２に示す。
Ｓ：水がコート面全体に一様に付着し、曇りは認められなかった
Ａ：コート面全体の１０％程度に曇りが認められた
Ｂ：コート面全体の３０％程度に曇りが認められた
Ｃ：コート面全体の５０％程度に曇りが認められた
Ｄ：水滴が付着しており、著しい曇りが認められた
Ｅ：塗膜が溶解した
[Persistent anti-fogging property of coating film]
The prepared antifogging agent was coated on a 5 mm thick glass plate with a Mayer bar so that the thickness of the dried coating film was 2 μm, and dried at 70 ° C. for 1 minute to obtain a coated glass plate. The coated glass plate was immersed in water at 40 ° C. for 1 week and then dried at 70 ° C. for 1 minute. Cover the mouth of a 200 mL beaker containing 100 mL of warm water at 40 ° C. with the coated glass plate subjected to the above treatment, and leave it in a 40 ° C. atmosphere for 24 hours. Then, visually observe the adhesion of water droplets on the coated surface. Judgment was made according to criteria. The results are shown in Table 2.
S: Water uniformly adhered to the entire coated surface, and no cloudiness was observed. A: Cloudiness was observed on about 10% of the entire coated surface. B: Cloudiness was observed on about 30% of the entire coated surface. C: About 50% of the entire coating surface was clouded D: Water droplets were attached and significant clouding was observed E: The coating film was dissolved
［塗膜のガラスへの密着性］
上記調製した防曇剤を５ｍｍ厚のガラス板上に、乾燥後の塗膜厚みが２μｍになるようにメイヤーバーでコートし、１２０℃で１分間、乾燥した。室温にて２４時間放置後、ＪＩＳ Ｋ５４００ ８．５．２の方法で密着性試験を行った。塗膜をカットして１ｍｍ×１ｍｍ×１００個の碁盤目部分を作成し、これを粘着テープにより引き剥がし、１００個の碁盤目中で剥離せず残っている個数により評価した。「ｎ／１００」は、１００個の碁盤目中のｎ個が剥離せず残っていることを示し、「１００／１００」は全く剥離しておらず、最も密着性の良いことを示す。評価は以下の基準に従って判定した。結果を表２に示す。
[Adhesion of coated film to glass]
The prepared antifogging agent was coated on a 5 mm thick glass plate with a Mayer bar so that the coating thickness after drying was 2 μm, and dried at 120 ° C. for 1 minute. After being allowed to stand at room temperature for 24 hours, an adhesion test was conducted by the method of JIS K5400 8.5.2. The coated film was cut to prepare 1 mm × 1 mm × 100 grid sections, which were peeled off with an adhesive tape, and evaluated based on the number remaining without peeling in the 100 grids. “N / 100” indicates that n of the 100 grids remain without being peeled off, and “100/100” indicates that they are not peeled off at all and have the best adhesion. Evaluation was determined according to the following criteria. The results are shown in Table 2.
Ａ：１００／１００
Ｂ：９０／１００以上１００／１００未満
Ｃ：８０／１００以上９０／１００未満
Ｄ：５０／１００以上８０／１００未満
Ｅ：５０／１００未満
A: 100/100
B: 90/100 or more and less than 100/100 C: 80/100 or more and less than 90/100 D: 50/100 or more and less than 80/100 E: Less than 50/100
［防曇剤の粘度安定性］
上記調製した防曇剤を２０℃恒温槽中に放置し、この防曇剤の温度が２０℃になった直後の粘度と７日後の粘度を測定した。防曇剤の温度が２０℃になった直後の粘度で７日後の粘度を除した値（７日後／直後）を求め、これを粘度比（倍）とし、以下の基準にしたがって判定した。結果を表２に示す。
Ａ：２．５倍未満
Ｂ：２．５倍以上３．５倍未満
Ｃ：３．５倍以上５．０倍未満
Ｄ：５．０倍以上であるが、防曇剤はゲル化していない
Ｅ：防曇剤は流動性を失いゲル化している
[Viscosity stability of antifogging agent]
The antifogging agent prepared above was left in a constant temperature bath at 20 ° C., and the viscosity immediately after the temperature of the antifogging agent reached 20 ° C. and the viscosity after 7 days were measured. A value obtained by dividing the viscosity after 7 days by the viscosity immediately after the temperature of the antifogging agent reached 20 ° C. (after 7 days / immediately) was obtained, and this was determined as the viscosity ratio (times), and was determined according to the following criteria. The results are shown in Table 2.
A: Less than 2.5 times B: 2.5 times or more and less than 3.5 times C: 3.5 times or more and less than 5.0 times D: 5.0 times or more, but the antifogging agent is not gelled E: Antifogging agent loses fluidity and gels
［実施例２〜２１及び比較例１〜１５］
実施例１において用いたＰＶＡ１に代えて、表２に示したＰＶＡを用いた以外は、実施例１と同様にして防曇剤を調製し、評価した。その結果を表２に併せて示す。
[Examples 2 to 21 and Comparative Examples 1 to 15]
An antifogging agent was prepared and evaluated in the same manner as in Example 1 except that PVA shown in Table 2 was used instead of PVA1 used in Example 1. The results are also shown in Table 2.
表２に示されるように、実施例１〜２１で調製した防曇剤（ＰＶＡ１〜２１）は、十分な水溶性及び粘度安定性を有し、得られる塗膜の防曇性、持続的防曇性及びガラスへの密着性に優れることが分かる。ここで、粘度安定性はＤ以上であれば実用上十分な粘度安定性を有しているとし、他の３項目が全てＣ以上であることがより優れている評価とする。さらに、ＰＶＡの粘度平均重合度（Ｐ）、けん化度、単量体単位の構造、含有率（Ｓ）、粘度平均重合度（Ｐ）と含有率（Ｓ）の積（Ｐ×Ｓ）を特定した、実施例１、９、１０、１５〜１８、２１の防曇剤は、得られた塗膜の防曇性、持続的防曇性及びガラスへの密着性、並びに粘度安定性に特に優れている（粘度安定性がＣ以上の評価であり、他の３項目中、２項目以上がＡであり、その他がＢである）。なお、実施例２〜８、１１〜１４、１９、２０は、得られた塗膜の防曇性、持続的防曇性、ガラスへの密着性、並びに粘度安定性等が若干低下することが分かる。これは粘度平均重合度（Ｐ）やけん化度の低下、単量体単位の構造が異なること、粘度平均重合度（Ｐ）と含有率（Ｓ）の積（Ｐ×Ｓ）が小さく、または大きくなること等に起因していると考えられる。 As shown in Table 2, the antifogging agents (PVA1 to 21) prepared in Examples 1 to 21 have sufficient water solubility and viscosity stability, and the resulting coating film has antifogging and continuous antifogging properties. It turns out that it is excellent in cloudiness and the adhesiveness to glass. Here, if the viscosity stability is D or more, it is assumed that it has practically sufficient viscosity stability, and the other three items are all evaluated to be C or more. Furthermore, PVA viscosity average polymerization degree (P), saponification degree, monomer unit structure, content rate (S), and product of viscosity average polymerization degree (P) and content rate (S) (P × S) are specified. The antifogging agents of Examples 1, 9, 10, 15 to 18, and 21 were particularly excellent in the antifogging properties, the persistent antifogging properties and the adhesion to glass, and the viscosity stability of the obtained coating films. (Viscosity stability is an evaluation of C or more, and among the other three items, two or more items are A and the others are B). In Examples 2 to 8, 11 to 14, 19 and 20, the anti-fogging property, continuous anti-fogging property, adhesion to glass, and viscosity stability of the obtained coating film may be slightly reduced. I understand. This is because the viscosity average degree of polymerization (P) and the degree of saponification are reduced, the structure of the monomer unit is different, and the product (P × S) of the viscosity average degree of polymerization (P) and the content (S) is small or large. It is thought that it originates in becoming.
一方、ＰＶＡが規定の要件を満たさない場合（比較例１〜１５）、実用上十分な粘度安定性を有さなかったり、得られた塗膜の防曇性、持続的防曇性及びガラスへの密着性が低下することが分かる。 On the other hand, when PVA does not satisfy the prescribed requirements (Comparative Examples 1 to 15), it does not have practically sufficient viscosity stability, or the resulting coating film has antifogging properties, continuous antifogging properties and glass. It turns out that the adhesiveness of is lowered.
本発明の防曇剤は、十分な取扱性及び粘度安定性を有し、得られる塗膜の防曇性、持続的防曇性及び基材への密着性に優れる。従って、当該防曇剤を用いて基材表面に積層される防曇層を備える透明部材は、防曇性及び持続的防曇性に優れる。 The antifogging agent of this invention has sufficient handling property and viscosity stability, and is excellent in the antifogging property of the coating film obtained, continuous antifogging property, and the adhesiveness to a base material. Therefore, a transparent member provided with an antifogging layer laminated on the substrate surface using the antifogging agent is excellent in antifogging properties and continuous antifogging properties.
Claims (7)
３７０≦Ｐ×Ｓ≦６，０００ ・・・（Ｉ）
Ｐ：粘度平均重合度
Ｓ：上記単量体単位の含有率（モル％） An antifogging agent comprising a vinyl alcohol polymer containing a monomer unit having a group represented by the following formula (1) and satisfying the following formula (I).
370 ≦ P × S ≦ 6,000 (I)
P: Viscosity average degree of polymerization S: Content of the monomer unit (mol%)
２００≦Ｐ≦４，０００ ・・・（ＩＩ）
０．１≦Ｓ≦１０ ・・・（ＩＩＩ）
Ｐ：粘度平均重合度
Ｓ：上記単量体単位の含有率（モル％） The antifogging agent according to claim 1, wherein the vinyl alcohol polymer further satisfies the following formulas (II) and (III).
200 ≦ P ≦ 4,000 (II)
0.1 ≦ S ≦ 10 (III)
P: Viscosity average degree of polymerization S: Content of the monomer unit (mol%)
−ＣＯ−ＮＲ６−＊ ・・・（３）
（式（３）中、Ｒ６は、水素原子又は炭素数１〜５のアルキル基である。＊は、上記式（１）で表される基との結合箇所を示す。） Antifogging agent according to claim 3 in which X in the above formula (2) is represented by the following formula (3).
-CO-NR 6- * (3)
(In the formula (3), R 6 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. * Indicates a bonding position with the group represented by the above formula (1).)
請求項１から請求項６のいずれか１項に記載の防曇剤を用い、この基材表面に積層される防曇層と
を備える透明部材。 A transparent member provided with a transparent base material and the antifogging layer laminated | stacked on this base-material surface using the antifogging agent of any one of Claims 1-6 .
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