JP2014162058A - Hydrophilic rubber molding and manufacturing method thereof - Google Patents
Hydrophilic rubber molding and manufacturing method thereof Download PDFInfo
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- 238000010068 moulding (rubber) Methods 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 90
- 229910021331 inorganic silicon compound Inorganic materials 0.000 claims abstract description 9
- 229910002808 Si–O–Si Inorganic materials 0.000 claims abstract description 8
- 229920001971 elastomer Polymers 0.000 claims description 153
- 239000005060 rubber Substances 0.000 claims description 153
- 238000000034 method Methods 0.000 claims description 38
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 12
- 238000005859 coupling reaction Methods 0.000 claims description 12
- 229910000077 silane Inorganic materials 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 11
- 238000004381 surface treatment Methods 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 229920001821 foam rubber Polymers 0.000 claims description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical group C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 36
- 230000008961 swelling Effects 0.000 abstract description 19
- 238000005406 washing Methods 0.000 abstract description 10
- 230000003252 repetitive effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 58
- 239000003795 chemical substances by application Substances 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 27
- 239000003921 oil Substances 0.000 description 23
- 229920000642 polymer Polymers 0.000 description 16
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical group C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 125000005372 silanol group Chemical group 0.000 description 8
- 229920000459 Nitrile rubber Polymers 0.000 description 7
- 239000004816 latex Substances 0.000 description 7
- 229920000126 latex Polymers 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- -1 ACM Polymers 0.000 description 3
- 210000005056 cell body Anatomy 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- HXVJQEGYAYABRY-UHFFFAOYSA-N 1-ethenyl-4,5-dihydroimidazole Chemical compound C=CN1CCN=C1 HXVJQEGYAYABRY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- GDFCSMCGLZFNFY-UHFFFAOYSA-N Dimethylaminopropyl Methacrylamide Chemical compound CN(C)CCCNC(=O)C(C)=C GDFCSMCGLZFNFY-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PYPQFOINVKFSJD-UHFFFAOYSA-N S[S] Chemical compound S[S] PYPQFOINVKFSJD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920006168 hydrated nitrile rubber Polymers 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001709 polysilazane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- AAYRWMCIKCRHIN-UHFFFAOYSA-N propane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCCS(O)(=O)=O AAYRWMCIKCRHIN-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Abstract
Description
本発明は、親水性ゴム成形体及びその製造方法に関する。 The present invention relates to a hydrophilic rubber molded body and a method for producing the same.
ゴム成形体は、様々な特性を有することから、ゴム手袋、ホース、履物、タイヤ、各種パッキン材料、塗料等を始め、様々な場面で使用されている。ここで、ゴム成形体を、自動車や自転車用のパーツ等として用いた場合、ゴム成形体には、グリース等の油汚れが蓄積される。その他にも、油汚れの付着した食器を洗浄する際に、排水口用ゴムカバーに油汚れが付着する。このように、油性材料が付着し得る用途に用いられたゴム成形体には、油汚れが蓄積され、劣化が促進されるため、定期的な整備や洗浄が必要となるが、ゴム成形体が疎水性であると、油と馴染み易く、油汚れを除去することが困難な場合がある。このような問題に対して、例えば、フッ素コート剤による表面処理を施しゴム成形体に親水性を与えることで、ゴム成形体表面に蓄積された油汚れを比較的容易に除去することも可能な親水性ゴム成形体が開発されている。 Rubber molded products have various properties and are used in various situations including rubber gloves, hoses, footwear, tires, various packing materials, paints, and the like. Here, when the rubber molded body is used as a part for automobiles or bicycles, oil contamination such as grease is accumulated in the rubber molded body. In addition, when cleaning dishes with oil stains, oil stains adhere to the drain cover rubber cover. As described above, the rubber molded body used for the application to which the oil-based material can adhere accumulates oil stains and promotes deterioration, and therefore requires regular maintenance and cleaning. If it is hydrophobic, it is easy to become familiar with oil and it may be difficult to remove oil stains. For such problems, for example, by applying a surface treatment with a fluorine coating agent to impart hydrophilicity to the rubber molded body, oil stains accumulated on the surface of the rubber molded body can be removed relatively easily. Hydrophilic rubber moldings have been developed.
また、ゴム成形体に親水性を与えるための方法としては、例えば、特許文献１には、有機過酸化物を配合した未加硫ゴム成形物と親水性のラジカル重合性モノマーを接触させ、該有機過酸化物の活性点以上の温度で加熱することで、比較的簡単にゴム成形体に親水化処理を行う方法が記載されている。また、特許文献２には、シリコーンゴムフィルムの表面を電子線等で処理してラジカルを形成し、この表面に親水性化合物を接触させてグラフトし、親水性にする方法が記載されている。 In addition, as a method for imparting hydrophilicity to a rubber molded body, for example, in Patent Document 1, an unvulcanized rubber molding compounded with an organic peroxide and a hydrophilic radical polymerizable monomer are brought into contact with each other. A method is described in which a rubber molding is subjected to a hydrophilic treatment relatively easily by heating at a temperature equal to or higher than the active point of the organic peroxide. Patent Document 2 describes a method in which a surface of a silicone rubber film is treated with an electron beam or the like to form radicals, and a hydrophilic compound is brought into contact with the surface for grafting to make it hydrophilic.
しかし、これらの方法によって形成された親水性ゴム成形体は、表面の汚れ落ち性や繰り返し洗いに対する耐性という点で、改良点を有するものであり、更には、水に接触させた際に膨潤が生じ、膨潤性を設計に組み込む必要が生じ得るという問題があった。また、特許文献２に係る親水性ゴム成形体の製造方法は、グラフト重合処理を行うため、処理工程が複雑化・長時間化し易いという課題があった。 However, the hydrophilic rubber molded body formed by these methods has an improvement in terms of surface dirt removal resistance and resistance to repeated washing, and further, swelling when brought into contact with water. There has been the problem that it may arise and the need to incorporate swellability into the design. Further, the method for producing a hydrophilic rubber molded body according to Patent Document 2 has a problem that the treatment process is complicated and requires a long time because the graft polymerization treatment is performed.
前述の課題に関し、本発明者らは、処理工程が複雑なグラフト重合反応等を用いずとも、ゴム成形体の少なくとも表面に特定のプライマー層を設け、特定の方法を用いて当該プライマー層に特定のポリマーを結合させることにより、膨潤を抑え、表面の汚れ落ち性が高く、繰り返しの使用に対しても防汚性を発揮し得る親水性ゴム成形体を作成可能なことを見出し、本発明を完成させた。 Regarding the above-mentioned problems, the present inventors provide a specific primer layer on at least the surface of the rubber molded body without using a complicated graft polymerization reaction, etc., and specify the primer layer using a specific method. It was found that a hydrophilic rubber molded body capable of suppressing swelling, having high surface dirt removal properties, and exhibiting antifouling properties even after repeated use can be produced by binding the polymer of the present invention. Completed.
即ち、本発明によれば、ゴム成形体の表面の少なくとも一部に存在し、Ｓｉ−Ｏ−Ｓｉで表されるシロキサン結合又はＳｉ−ＮＨ−Ｓｉで表されるシラザン結合を骨格として有する網状構造の無機ケイ素化合物からなるプライマー層と、親水性ポリマーと、がシロキサン結合を介して結合している親水性ゴム成形体が提供される。
前記親水性ゴム成形体において、少なくとも一部の前記親水性ポリマーが、主鎖の末端のみで前記プライマー層と結合していることが好ましい。
前記親水性ゴム成形体において、少なくとも一部の前記親水性ポリマーが、ベタイン基を含む（メタ）アクリル酸エステルを有することが好ましい。
前記親水性ゴム成形体において、前記ベタイン基が、カルボキシベタイン基であることが好ましい。
前記親水性ゴム成形体において、前記親水性ポリマーの重量平均分子量が３００〜５００００であることが好ましい。
前記親水性ゴム成形体において、前記ゴム成形体が発泡体であってもよい。
前記親水性ゴム成形体において、前記発泡体が連続気泡を有していてもよい。
前記親水性ゴム成形体において、前記ゴム成形体がＮＢＲであることが好ましい。
また、本発明によれば、ゴム発泡体の表面の少なくとも一部を、水ガラス又はシラザンで処理することで、前記表面に水酸基を有する、Ｓｉ−Ｏ−Ｓｉで表されるシロキサン結合又はＳｉ−ＮＨ−Ｓｉで表されるシラザン結合を骨格として有する網状構造の無機ケイ素化合物からなるプライマー層を形成する表面処理工程と、親水性ポリマーを、シランカップリング反応により前記プライマー層の表面に結合させる親水化工程と、を含む親水性ゴム成形体の製造方法が提供される。
前記親水性ゴム成形体の製造方法において、前記親水化工程が、前記親水性ポリマーとして、主鎖の末端のみで前記プライマー層と結合可能な親水性ポリマーを用いて行う工程であることが好ましい。
前記親水性ゴム成形体の製造方法において、前記親水化工程が、前記親水性ポリマーとして、前記親水性ポリマーの少なくとも主鎖の一末端に加水分解性シリル基を導入されたものを用い、前記加水分解性シリル基を加水分解した後に前記親水性ポリマーをシランカップリング反応により前記プライマー層の前記水酸基と脱水縮合させることで前記表面に結合させる工程であることが好ましい。
前記親水性ゴム成形体の製造方法において、前記親水性ポリマーが、ベタイン基を含む（メタ）アクリル酸エステルを有することが好ましい。
前記親水性ゴム成形体の製造方法において、前記ベタイン基が、カルボキシベタイン基であることが好ましい。
前記親水性ゴム成形体の製造方法において、前記親水性ポリマーの重量平均分子量が３００〜５００００であることが好ましい。
前記親水性ゴム成形体の製造方法において、前記ゴム成形体が発泡体であってもよい。
前記親水性ゴム成形体の製造方法において、前記発泡体が連続気泡を有していてもよい。
前記親水性ゴム成形体の製造方法において、前記ゴム成形体がＮＢＲであることが好ましい。
That is, according to the present invention, a network structure having a siloxane bond represented by Si—O—Si or a silazane bond represented by Si—NH—Si as a skeleton is present on at least a part of the surface of the rubber molded body. There is provided a hydrophilic rubber molded article in which a primer layer made of the above inorganic silicon compound and a hydrophilic polymer are bonded via a siloxane bond.
In the hydrophilic rubber molded body, it is preferable that at least a part of the hydrophilic polymer is bonded to the primer layer only at the end of the main chain.
In the hydrophilic rubber molded body, it is preferable that at least a part of the hydrophilic polymer has a (meth) acrylic acid ester containing a betaine group.
In the hydrophilic rubber molded body, the betaine group is preferably a carboxybetaine group.
In the hydrophilic rubber molded body, the hydrophilic polymer preferably has a weight average molecular weight of 300 to 50,000.
In the hydrophilic rubber molded body, the rubber molded body may be a foam.
In the hydrophilic rubber molded body, the foam may have open cells.
In the hydrophilic rubber molded body, the rubber molded body is preferably NBR.
Further, according to the present invention, at least a part of the surface of the rubber foam is treated with water glass or silazane so that the surface has a hydroxyl group, a siloxane bond represented by Si—O—Si, or Si—. A surface treatment step of forming a primer layer made of a network-structured inorganic silicon compound having a silazane bond represented by NH—Si as a skeleton, and a hydrophilic property for binding a hydrophilic polymer to the surface of the primer layer by a silane coupling reaction And a process for producing a hydrophilic rubber molded body.
In the method for producing a hydrophilic rubber molded body, the hydrophilization step is preferably a step performed using a hydrophilic polymer that can be bonded to the primer layer only at the end of the main chain as the hydrophilic polymer.
In the method for producing a hydrophilic rubber molded body, the hydrophilization step uses, as the hydrophilic polymer, a hydrolyzable silyl group introduced at least at one end of the main chain of the hydrophilic polymer, It is preferable that after the degradable silyl group is hydrolyzed, the hydrophilic polymer is bonded to the surface by dehydration condensation with the hydroxyl group of the primer layer by a silane coupling reaction.
In the method for producing a hydrophilic rubber molded body, the hydrophilic polymer preferably has a (meth) acrylic acid ester containing a betaine group.
In the method for producing the hydrophilic rubber molded body, the betaine group is preferably a carboxybetaine group.
In the method for producing the hydrophilic rubber molded body, the hydrophilic polymer preferably has a weight average molecular weight of 300 to 50,000.
In the method for producing the hydrophilic rubber molded body, the rubber molded body may be a foam.
In the method for producing the hydrophilic rubber molded body, the foam may have open cells.
In the method for producing the hydrophilic rubber molded body, the rubber molded body is preferably NBR.
本発明によれば、複雑な前処理工程を要さず、汚れ落ち性が高く、繰り返し水洗しても親水性が低下し難く、水の接触による膨潤率が低い親水性ゴム成形体を提供することが可能である。 According to the present invention, there is provided a hydrophilic rubber molded body that does not require a complicated pretreatment step, has high dirt removal properties, is not easily lowered in hydrophilicity even when repeatedly washed with water, and has a low swelling rate due to contact with water. It is possible.
以下、本形態に係る親水性ゴム成形体の、構造、物性、製造方法及び用途等に関して順次説明するが、本形態はこれらによって何ら限定されない。 Hereinafter, the structure, physical properties, manufacturing method, application, and the like of the hydrophilic rubber molded body according to the present embodiment will be described in order, but the present embodiment is not limited by these.
≪親水性ゴム成形体の構造等≫
初めに、本形態に係る親水性ゴム成形体の構造に関して説明する。本形態に係る親水性ゴム成形体は、ゴム成形体の表面の少なくとも一部（全表面でもよい）に存在し、Ｓｉ−Ｏ−Ｓｉで表されるシロキサン結合又はＳｉ−ＮＨ−Ｓｉで表されるシラザン結合を骨格として有する網状構造の無機ケイ素化合物からなるプライマー層と、親水性ポリマーと、がシロキサン結合を介して結合している、親水性ゴム成形体に関する。以下に、本形態に係る親水性ゴム成形体の構成材料である、ゴム成形体、プライマー層及び親水性ポリマーに関して説明する。
≪Structure etc. of hydrophilic rubber moldings≫
First, the structure of the hydrophilic rubber molded body according to this embodiment will be described. The hydrophilic rubber molded body according to this embodiment is present on at least a part (or the entire surface) of the surface of the rubber molded body, and is represented by a siloxane bond represented by Si—O—Si or Si—NH—Si. The present invention relates to a hydrophilic rubber molded body in which a primer layer made of a network-structured inorganic silicon compound having a silazane bond as a skeleton and a hydrophilic polymer are bonded via a siloxane bond. Hereinafter, the rubber molded body, the primer layer, and the hydrophilic polymer, which are constituent materials of the hydrophilic rubber molded body according to this embodiment, will be described.
＜ゴム成形体＞
本形態に係る親水性ゴム成形体の芯材である、ゴム成形体について説明する。尚、本形態に係るゴム成形体は、親水性ゴム成形体の用途に合わせて、所望の形状や大きさとしてよい。また、本形態に係るゴム成形体は、平滑面を有するゴム成形体や凹凸のあるゴム成形体等の何れでもよく、表面状態も限定されない。
<Rubber molding>
The rubber molded body which is the core material of the hydrophilic rubber molded body according to this embodiment will be described. Note that the rubber molded body according to the present embodiment may have a desired shape and size in accordance with the use of the hydrophilic rubber molded body. Moreover, the rubber molded body according to the present embodiment may be any of a rubber molded body having a smooth surface, a rubber molded body having irregularities, and the like, and the surface state is not limited.
（組成）
本実施形態に係るゴム成形体としては、ＮＢＲ、ＨＮＢＲ、ＦＫＭ、ＡＣＭ、ＶＭＱ、ＡＵ、ＥＰＤＭ、ＣＲ、ＣＳＭ、ＣＯ、ＮＲ、ＩＲ、ＳＢＲ、ＢＲ、Ｔ、ＮＯＲ、ＴＰＥ等、一般に使用されるゴムからなる様々なものを好適に適用可能であるが、耐油性、引張り強さ、耐磨耗性等に優れるという観点から、ＮＢＲであることがより好適である。
(composition)
As the rubber molded body according to this embodiment, NBR, HNBR, FKM, ACM, VMQ, AU, EPDM, CR, CSM, CO, NR, IR, SBR, BR, T, NOR, TPE, etc. are generally used. Various materials made of rubber can be suitably applied, but NBR is more preferable from the viewpoint of excellent oil resistance, tensile strength, abrasion resistance, and the like.
（発泡）
ゴム成形体の構造としては、非発泡であるソリッド形状に限らず、発泡構造であってもよく、更に当該発泡構造としては、独立気泡であっても連続気泡であってもよく、用途に合わせて適宜使用可能である。
(Foam)
The structure of the rubber molded body is not limited to a solid shape that is not foamed, and may be a foamed structure. Further, the foamed structure may be closed cells or open cells. Can be used as appropriate.
＜プライマー層＞
前述のように、本形態に係る親水性ゴム成形体のプライマー層は、ゴム成形体の表面に存在し、無機ケイ素結合からなり、当該プライマー層と親水性ポリマーとがシロキサン結合又はシラザン結合を介して結合することで、ゴム成形体に親水性を付与する。
<Primer layer>
As described above, the primer layer of the hydrophilic rubber molded body according to this embodiment is present on the surface of the rubber molded body and is composed of an inorganic silicon bond, and the primer layer and the hydrophilic polymer are bonded via a siloxane bond or a silazane bond. To give hydrophilicity to the rubber molded body.
（組成）
本形態に係るプライマー層は、無機ケイ素結合を有し、当該無機ケイ素結合は、Ｓｉ−Ｏ−Ｓｉで表されるシロキサン結合又はＳｉ−ＮＨ−Ｓｉで表されるシラザン結合を骨格とする。プライマー層がこの骨格を基本とする網目構造を有しており、当該網目に存在する多数の結合点を介して親水性ポリマーが結合することで、多数の親水性ポリマーを強固に結合させることが可能となる（即ち、結合しないポリマー量を低減させることができ、結果、ゴム成形体から親水性ポリマーが流れ落ちずに存在してくれるようになる）。
(composition)
The primer layer according to the present embodiment has an inorganic silicon bond, and the inorganic silicon bond has a siloxane bond represented by Si—O—Si or a silazane bond represented by Si—NH—Si as a skeleton. The primer layer has a network structure based on this skeleton, and the hydrophilic polymer is bonded through a large number of bonding points existing in the network, whereby a large number of hydrophilic polymers can be firmly bonded. (I.e., the amount of unbound polymer can be reduced, and as a result, the hydrophilic polymer is present without flowing off from the rubber molded body).
（網状構造）
本形態に係るプライマー層の無機ケイ素結合は、網状構造を有している。共有結合という強固な結合で網目状の無機ケイ素結合が形成されているため、親水性ゴム成形体において水による膨潤が抑制される。また、無機ケイ素結合が網状構造であることにより親水性ポリマーが広い範囲で結合することが可能となる（換言すれば、多数の結合点を有している）ため、親水性ゴム成形体の親水性・汚れ落ち性が向上する。また、本形態によれば、網目上の多数の結合点に親水性ポリマーが結合していること（換言すれば、結合していない親水性ポリマーの量が少ないこと）に加え、プライマー層のゴム成形体への密着性が高く、プライマー層（＋それに結合した親水性ポリマー）の剥離が抑制されるため、親水性ゴム成形体の繰り返し洗浄に対する耐性を向上させることが可能となる。尚、網状構造の無機ケイ素化合物とは、当業界にて周知の通り、無機ケイ素化合物のシロキサン結合又はシラザン結合が、多数の点で交差・結合し、網目のように広がり、２次・３次構造を形成していることを示す。
(Network structure)
The inorganic silicon bond of the primer layer according to this embodiment has a network structure. Since a network-like inorganic silicon bond is formed by a strong bond called a covalent bond, swelling with water is suppressed in the hydrophilic rubber molded body. Further, since the inorganic silicon bond has a network structure, the hydrophilic polymer can be bonded in a wide range (in other words, it has a large number of bonding points). And dirt removal properties are improved. In addition, according to this embodiment, the hydrophilic polymer is bonded to many bonding points on the network (in other words, the amount of the hydrophilic polymer not bonded is small), and the rubber of the primer layer Since the adhesiveness to the molded body is high and the peeling of the primer layer (+ the hydrophilic polymer bonded thereto) is suppressed, it is possible to improve the resistance to repeated washing of the hydrophilic rubber molded body. The inorganic silicon compound having a network structure is, as is well known in the art, the siloxane bond or silazane bond of the inorganic silicon compound crosses and bonds at a number of points and spreads like a network. It shows that a structure is formed.
（層厚）
本形態に係るプライマー層の厚さは、特に規定されないが、例えば、好適には３ｎｍ〜１００μｍであり、より好適には１０ｎｍ〜２０ｎｍである。プライマー層厚が１００μｍを超えると、親水性ゴム成形体が変形した際に、変形に対する追従性が悪くなり、プライマー層にひび割れが生じ易くなることがある。プライマー層厚が３ｎｍ未満であると、プライマー層のゴム成形体に対する密着強度が不足し、繰り返し洗浄に対する十分な耐性が得られないことがある。
(Layer thickness)
Although the thickness of the primer layer which concerns on this form is not prescribed | regulated especially, For example, it is 3 nm-100 micrometers suitably, More preferably, it is 10 nm-20 nm. When the primer layer thickness exceeds 100 μm, when the hydrophilic rubber molded body is deformed, the followability to the deformation is deteriorated, and the primer layer may be easily cracked. If the primer layer thickness is less than 3 nm, the adhesion strength of the primer layer to the rubber molded product may be insufficient, and sufficient resistance to repeated cleaning may not be obtained.
＜親水性ポリマー＞
親水性ポリマーは、シロキサン結合を介してプライマー層と結合されている。当該シロキサン結合は、一つのポリマー構造に対して、１又は複数存在していてもよく、また主鎖及び側鎖のどのような箇所に存在していてもよい。ここで、一つのポリマー構造中に、プライマー層と結合している複数のシロキサン結合が存在する場合には、親水性ポリマーがより強くプライマー層に結合されているため繰り返し洗浄に対する耐性は高くなり得るが、親水性ゴム成形体が圧縮・変形した際等に、ポリマーが結合箇所から受ける荷重によって破断し、汚れ落とし性に劣り易くなり得る。他方、ポリマー構造中に、プライマー層との複数の結合箇所が存在しない場合には、そのような問題が生じ難い。尚、親水性ポリマーが、主鎖の末端のみでシロキサン結合を介してプライマー層と結合されている場合には、親水性ポリマーの周囲が水雰囲気となった際に、当該親水性ポリマーが末端結合部を足として大きく立ち上がり汚れを浮かび上がらせ、汚れ落とし性を向上させる効果が強くなるためより好適である。尚、当該親水性ポリマーとしては、ブラシ状の骨格を持つことがより好適である。
<Hydrophilic polymer>
The hydrophilic polymer is bonded to the primer layer via a siloxane bond. One or a plurality of the siloxane bonds may be present for one polymer structure, and may be present at any position of the main chain and the side chain. Here, when a plurality of siloxane bonds bonded to the primer layer are present in one polymer structure, the hydrophilic polymer is more strongly bonded to the primer layer, so that the resistance to repeated washing can be increased. However, when the hydrophilic rubber molded body is compressed or deformed, the polymer may be broken by a load received from the bonded portion, and the dirt removing property may be easily deteriorated. On the other hand, when a plurality of bonding sites with the primer layer do not exist in the polymer structure, such a problem hardly occurs. In addition, when the hydrophilic polymer is bonded to the primer layer through the siloxane bond only at the end of the main chain, the hydrophilic polymer is bonded to the end when the periphery of the hydrophilic polymer is in a water atmosphere. It is more preferable because the effect of improving the dirt removal property by increasing the height of the part by using the foot as a foot is increased. It is more preferable that the hydrophilic polymer has a brush-like skeleton.
（組成）
本形態に係る親水性ポリマーは、親水性を有する限り特に限定されず好適に適用可能である。例えば、アクリル酸、メタクリル酸、クロトン酸、アクリルアミドプロパンスルホン酸、ビニルホスホン酸、マレイン酸、ビニルスルホン酸及びそれらの塩や、アルカリ金属−及びアンモニウム塩の如き水溶性モノマー成分のホモ−及びコポリマー等が挙げられる。別のモノマー成分としては、アクリルアミド、Ｎ−ビニルアミド、アクリル−及びメタクリル酸のヒドロキシアルキルエステル並びに塩基性−及びカチオン性モノマー成分、例えばアクリル−及びメタクリル酸の塩基性エステル及びアミド、例えばジメチルアミノエタノールのエステル、又はＮ−ジメチルアミノプロピルメタクリルアミド並びにジメチルジアリルアンモニウムクロライド又はビニルイミダゾーリン等が挙げられる。ここで、本形態に係る親水性ポリマーとしては、強い親水性を発揮し得るという観点から、ベタイン基を有する（メタ）アクリル酸エステルであることがより好適であり、親水性をより強めるという観点から、カルボキシベタイン基を有する（メタ）アクリル酸エステルであることが更に好適である。尚、本形態において、親水性を有するとは、水雰囲気にて湿潤し得ることを示す。湿潤するとは、液体（例えば、水溶液）が試料内に浸透する、又はその表面に拡散することが可能であることを示す。
(composition)
The hydrophilic polymer according to this embodiment is not particularly limited as long as it has hydrophilicity, and can be suitably applied. For example, homo- and copolymers of water-soluble monomer components such as acrylic acid, methacrylic acid, crotonic acid, acrylamide propane sulfonic acid, vinyl phosphonic acid, maleic acid, vinyl sulfonic acid and their salts, alkali metal and ammonium salts, etc. Is mentioned. Other monomer components include acrylamide, N-vinyl amide, hydroxyalkyl esters of acrylic and methacrylic acid and basic and cationic monomer components such as basic esters and amides of acrylic and methacrylic acid such as dimethylaminoethanol. Examples thereof include esters, N-dimethylaminopropylmethacrylamide, dimethyldiallylammonium chloride, and vinylimidazoline. Here, the hydrophilic polymer according to the present embodiment is more preferably a (meth) acrylic acid ester having a betaine group from the viewpoint that strong hydrophilicity can be exhibited, and the viewpoint of further enhancing the hydrophilicity. Therefore, it is more preferable that it is a (meth) acrylic acid ester having a carboxybetaine group. In addition, in this embodiment, having hydrophilicity indicates that it can be wetted in a water atmosphere. Wetting indicates that a liquid (eg, an aqueous solution) can penetrate into the sample or diffuse to its surface.
ポリマーの重量平均分子量は、３００〜５００００であることが好適であり、５０００〜３００００であることがより好適である。重量平均分子量が３００未満であると、前述のような、親水性ポリマーの周囲が水雰囲気となった際に、当該親水性ポリマー結合部を足として立ち上がることによる、汚れ落とし性能（汚れを押し出す力）が十分に得られない。他方、重量平均分子量が５００００を超えると、水雰囲気下で膨潤が起こり易くなる。尚、当該重量平均分子量は、ゲル浸透クロマトグラフィ（ＧＰＣ）によって測定されたものを示す。 The weight average molecular weight of the polymer is preferably 300 to 50000, and more preferably 5000 to 30000. When the weight average molecular weight is less than 300, as described above, when the periphery of the hydrophilic polymer becomes a water atmosphere, dirt removal performance (force to push out the dirt) by standing up with the hydrophilic polymer binding part as a foot ) Cannot be obtained sufficiently. On the other hand, when the weight average molecular weight exceeds 50,000, swelling easily occurs in a water atmosphere. In addition, the said weight average molecular weight shows what was measured by the gel permeation chromatography (GPC).
≪親水性ゴム成形体の製造方法≫
次に、本形態に係る親水性ゴム成形体の製造工程として、製造工程、原料等に関して説明する。
≪Method for producing hydrophilic rubber molded body≫
Next, a manufacturing process, a raw material, etc. are demonstrated as a manufacturing process of the hydrophilic rubber molding which concerns on this form.
＜製造工程＞
本形態に係る親水性ゴム成形体の製造方法は、ゴム成形体に対してプライマー層を形成する表面処理工程と、当該プライマー層に、シランカップリング反応により親水性ポリマーを結合させる親水化工程と、を含む。以下、それぞれに関して詳述する。尚、本形態に係る親水性ゴム成形体の製造方法においては、更に当該表面処理工程の前に、ゴム成形体の不純物を取り除く脱脂工程等を有していてもよい。
<Manufacturing process>
The method for producing a hydrophilic rubber molded body according to the present embodiment includes a surface treatment process for forming a primer layer on the rubber molded body, and a hydrophilization process for binding a hydrophilic polymer to the primer layer by a silane coupling reaction. ,including. Each will be described in detail below. In addition, in the manufacturing method of the hydrophilic rubber molding which concerns on this form, you may have the degreasing process etc. which remove the impurity of a rubber molding further before the said surface treatment process.
（表面処理工程）
液状のプライマー剤をゴム成形体の少なくとも一部の表面に適用した後、乾燥させ、ゴム成形体の当該表面を、水酸基が表面に存在するプライマー層で被覆する。以下に表面処理工程における諸条件を説明する。
・原料（１）プライマー剤
プライマーは、Ｓｉ−Ｏ−Ｓｉで表されるシロキサン結合又はＳｉ−ＮＨ−Ｓｉで表されるシラザン結合を骨格として有する無機ケイ素化合物を形成し得るものであれば限定されず、例えば水ガラス（この場合、プライマー層はシロキサン結合が骨格となる）やシラザン（この場合、プライマー層はシラザン結合が骨格となる）等を好適に使用可能である。尚、プライマーが高粘度の場合等、溶媒（希釈剤）を適宜用いてもよい。
・プロセス
ゴム成形体にプライマー剤を適用する方法としては、例えば、プライマー剤中にゴム成形体を含侵する方法でも、スプレーコート等の方法でゴム成形体にプライマー剤を塗布するといった方法でもよく、何ら限定されない。尚、当該ゴム成形体を親水化工程により親水化処理を施す際には、プライマー剤により湿ったままの状態としても、乾燥させてもよい。プライマー剤の温度や作業環境等も特に限定されないが、例えば、３０℃以下の環境としてもよい。プライマーを乾燥させる場合にも、乾燥方法は限定されず、空気中に放置しても熱風機等を用いた乾燥（例えば、３０℃以下の送風による乾燥）であってもよい。ここで、表面処理工程としては、必要であれば当該プライマー層の表面に水酸基を形成するための工程を更に含んでいてもよく、このような工程を要する場合にも、プライマー層の表面に水酸基を形成し得る工程であれば、選択した原料等の性質に合わせ適宜自由に選択可能である。例えば、ゴム成形体にプライマー層を形成した後に、当該プライマー層を気中に晒す工程等が考え得るが、プライマー層を形成した段階でプライマー層の表面に水酸基が形成される等の場合には、このような工程は必ずしも必要ではない。
(Surface treatment process)
The liquid primer is applied to at least a part of the surface of the rubber molded body, and then dried, and the surface of the rubber molded body is covered with a primer layer having hydroxyl groups on the surface. Various conditions in the surface treatment process will be described below.
・ Raw material (1) Primer The primer is limited as long as it can form an inorganic silicon compound having a siloxane bond represented by Si—O—Si or a silazane bond represented by Si—NH—Si as a skeleton. For example, water glass (in this case, the primer layer has a siloxane bond as a skeleton) or silazane (in this case, the primer layer has a silazane bond as a skeleton) can be preferably used. In addition, you may use a solvent (diluent) suitably, when a primer is highly viscous.
Process As a method of applying the primer agent to the rubber molded body, for example, a method of impregnating the rubber molded body in the primer agent or a method of applying the primer agent to the rubber molded body by a method such as spray coating may be used. There is no limitation. When the rubber molded body is subjected to a hydrophilic treatment in the hydrophilic step, the rubber molded body may be kept wet with the primer agent or may be dried. The temperature and working environment of the primer agent are not particularly limited, but may be an environment of 30 ° C. or lower, for example. Even when the primer is dried, the drying method is not limited, and it may be left in the air or dried using a hot air blower (for example, drying by blowing air of 30 ° C. or less). Here, if necessary, the surface treatment step may further include a step for forming a hydroxyl group on the surface of the primer layer. Even when such a step is required, a hydroxyl group is formed on the surface of the primer layer. Can be selected as appropriate according to the properties of the selected raw material and the like. For example, a step of exposing the primer layer to the air after forming the primer layer on the rubber molded body can be considered, but in the case where a hydroxyl group is formed on the surface of the primer layer at the stage of forming the primer layer, etc. Such a process is not always necessary.
（親水化工程）
表面処理工程においてゴム発泡体の少なくとも一部の表面を被覆したプライマー層に、シランカップリング反応により親水性ポリマーを結合させることで、ゴム発泡体に親水性を与える。以下に親水化工程における諸条件を説明する。
・原料（２）親水性ポリマー
本形態に係る親水性ゴム成形体の製造方法における、親水性ポリマーの組成等に関しては上述した通りであるので、ここでは詳細な説明を省略する。
・原料（３）シランカップリング剤
親水化工程で用いられるシランカップリング剤としては、プライマー層及び親水性ポリマーとの結合性を有するものであれば、どのようなものでも使用可能である。例えば、有機官能基として、アミノ、ビニル、メタクリル、イソシアネート、メルカプト、サルファー、ウレイド、エポキシ等から、加水分解基として、メトキシ、エトキシ、メトキシエトキシ等から、適宜選択し、シランカップリング剤とすればよい。
・プロセス
前記表面処理工程を経てプライマー層が形成されたゴム成形体に、親水化処理剤を適用する方法としては、例えば、親水化処理剤中にゴム成形体を含侵する方法でも、スプレーコート等の方法でゴム成形体に親水化処理剤を塗布するといった方法でもよく、何ら限定されない。その後、例えばオーブンで加熱（例えば８０℃１時間）する等し、ゴム成形体表面（プライマー層）に存在する水酸基を結合手として、ゴム成形体のプライマー層と親水性ポリマーとを、シランカップリング反応により結合させる。尚、親水化工程におけるプロセス条件（例えば、オーブン温度や加熱時間等）は特に限定されず、カップリング剤の種類やゴム成形体の種類等に応じて適宜設定可能である。
(Hydrophilic process)
In the surface treatment step, hydrophilic property is imparted to the rubber foam by bonding a hydrophilic polymer to the primer layer covering at least a part of the surface of the rubber foam by a silane coupling reaction. Various conditions in the hydrophilization process will be described below.
-Raw material (2) hydrophilic polymer Since the composition of the hydrophilic polymer and the like in the method for producing a hydrophilic rubber molded body according to the present embodiment are as described above, detailed description thereof is omitted here.
Raw Material (3) Silane Coupling Agent Any silane coupling agent used in the hydrophilization step can be used as long as it has binding properties with the primer layer and the hydrophilic polymer. For example, as an organic functional group, amino, vinyl, methacryl, isocyanate, mercapto, sulfur, ureido, epoxy, etc., and as a hydrolyzing group, methoxy, ethoxy, methoxyethoxy, etc. are appropriately selected, and a silane coupling agent can be used. Good.
-Process As a method of applying a hydrophilizing agent to the rubber molded body on which the primer layer has been formed through the surface treatment step, for example, a method of impregnating the rubber molded body in the hydrophilizing agent may be spray coating. A method of applying a hydrophilic treatment agent to the rubber molded body by a method such as the above may be used, and the method is not limited at all. Then, for example, heating in an oven (for example, 80 ° C. for 1 hour), and using the hydroxyl group present on the surface of the rubber molded body (primer layer) as a bond, the primer layer of the rubber molded body and the hydrophilic polymer are coupled with silane coupling. Combine by reaction. In addition, the process conditions (for example, oven temperature, heating time, etc.) in a hydrophilization process are not specifically limited, It can set suitably according to the kind of coupling agent, the kind of rubber molded object, etc.
尚、親水化工程としては、上述のように、（第一の手法）プライマー層に対してシランカップリング剤を用いたシランカップリング処理を行い、次にシランカップリング処理された層に対して親水性ポリマーを結合させてもよいし、（第二の手法）予めシランカップリング剤と親水性ポリマーを重合させることでシラノール基含有親水性ポリマーを形成し、当該シラノール基含有親水性ポリマーをプライマー層に結合させるシランカップリング工程を含むものであってもよい。更には、（第三の手法）プライマー層に対してシランカップリング剤を用いたシランカップリング処理を行い、次に親水性モノマー（場合により疎水性モノマーを添加してもよい）を重合させて親水性ポリマー基を形成させる工程であってもよい。但し、処理工程の単純化及び短時間化の観点からは、第二の手法が好適である。また、第二の手法は、親水性ポリマーの主鎖の末端のみにシラノール基を位置させるように制御し易いため、親水性ポリマーの主鎖の末端のみでプライマー層とシロキサン結合されるよう制御し易くなるという観点からも好適である。 As described above, as the hydrophilization step, as described above (first method), the primer layer is subjected to silane coupling treatment using a silane coupling agent, and then to the silane coupling treatment layer. A hydrophilic polymer may be bonded, or (second method) a silanol group-containing hydrophilic polymer is formed by previously polymerizing a silane coupling agent and a hydrophilic polymer, and the silanol group-containing hydrophilic polymer is used as a primer. It may include a silane coupling step for bonding to the layer. Furthermore, (third method) silane coupling treatment using a silane coupling agent is performed on the primer layer, and then a hydrophilic monomer (a hydrophobic monomer may be added in some cases) is polymerized. It may be a step of forming a hydrophilic polymer group. However, the second method is preferable from the viewpoint of simplifying the processing steps and shortening the processing time. In addition, since the second method is easy to control so that the silanol group is located only at the end of the main chain of the hydrophilic polymer, control is performed so that the primer layer is bonded to the primer layer only at the end of the main chain of the hydrophilic polymer. It is also preferable from the viewpoint that it becomes easy.
本形態に係る親水性ゴム成形体の製造方法によれば、少なくともゴム成形体の表面の一部に、共有結合という強固な結合で、網目状の無機ケイ素結合を形成可能であるため、前述のように、親水性ゴム成形体において水による膨潤が抑制される。また、前述のように、親水性ポリマーが広い範囲で結合することが可能となる（換言すれば、網目上の多数の結合点と結合する）ため、親水性ゴム成形体の親水性・汚れ落ち性が向上する。また、結合していない親水性ポリマー量を低減できると共にプライマー層のゴム成形体への密着性を高くすることが可能であるため、結合していない親水性ポリマーの流出やプライマー層の剥離に起因した親水性の低下を防止でき、親水性ゴム成形体の繰り返し洗浄に対する耐性を向上させることが可能となる。尚、例えばゴム成形体を気泡体（特に連泡体）とした場合にも、表層に近い部分に親水性ポリマーを存在させ、ゴム成形体の内部には親水性ポリマーが存在しないようにすることが可能であるため、親水性ゴム成形体を水に含侵した際にも、ゴム成形体の内部で親水性ポリマーが水を吸着し膨潤することを防ぎ、低膨潤性の親水性ゴム成形体を得ることが可能となる。 According to the method for producing a hydrophilic rubber molded body according to the present embodiment, a network-like inorganic silicon bond can be formed on at least a part of the surface of the rubber molded body by a strong bond called a covalent bond. Thus, the swelling by water is suppressed in the hydrophilic rubber molded body. Further, as described above, the hydrophilic polymer can be bonded in a wide range (in other words, bonded to a large number of bonding points on the network). Improves. In addition, the amount of unbound hydrophilic polymer can be reduced and the adhesion of the primer layer to the rubber molded body can be increased, resulting in outflow of unbound hydrophilic polymer and peeling of the primer layer. Thus, it is possible to prevent the decrease in hydrophilicity and to improve the resistance to repeated washing of the hydrophilic rubber molded body. For example, even when the rubber molded body is a foam (particularly a continuous foam), the hydrophilic polymer should be present near the surface layer so that the hydrophilic polymer does not exist inside the rubber molded body. Therefore, even when the hydrophilic rubber molded body is impregnated with water, the hydrophilic polymer prevents water from adsorbing and swelling inside the rubber molded body, and the low-swelling hydrophilic rubber molded body. Can be obtained.
≪親水性ゴム成形体の物性≫
次に、本形態に係る親水性ゴム成形体の物性に関して説明する。本形態に係る親水性ゴム成形体は、低い膨潤率、高い水洗い後ポリマー残留率、高い親水性・高い油汚れ落ち性を有する。
≪Physical properties of hydrophilic rubber moldings≫
Next, physical properties of the hydrophilic rubber molded body according to this embodiment will be described. The hydrophilic rubber molded body according to the present embodiment has a low swelling rate, a high polymer residual rate after washing with water, a high hydrophilic property and a high oil stain removal property.
＜膨潤率＞
膨潤は、ゴム成形体（特に連泡体）を水に浸漬した場合に構造内部に水分をため込むことで生じる。即ち、ゴム成形体の親水性が高い程膨潤率が高くなり得るが、本形態に係る親水性ゴム成形体は、前述のように、共有結合という強固な結合で網目状の無機ケイ素結合が形成されていることから、膨潤率が低く抑えられている。更には、本形態に係る製造方法でゴム成形体を製造した場合、プライマー層の網目構造には多数の結合点が存在するため、使用する親水性ポリマーの大部分がプライマー層に結合する結果、ゴム成形体（特に連泡体）の内部には親水性ポリマーが殆ど侵入しないと理解される。これによっても、即ち、内部に存在する親水性ポリマーが殆ど存在しないことによっても、膨潤が抑制されると考えられる。
<Swelling rate>
Swelling occurs when water is accumulated in the structure when a rubber molded body (particularly, open cell body) is immersed in water. That is, the higher the hydrophilicity of the rubber molded body, the higher the swelling ratio. However, as described above, the hydrophilic rubber molded body according to this embodiment forms a network-like inorganic silicon bond by a strong bond called a covalent bond as described above. Therefore, the swelling rate is kept low. Furthermore, when a rubber molded body is produced by the production method according to the present embodiment, since a large number of bonding points exist in the network structure of the primer layer, most of the hydrophilic polymer to be used is bonded to the primer layer. It is understood that the hydrophilic polymer hardly penetrates into the rubber molded body (in particular, the open cell body). It is considered that the swelling is also suppressed by this, that is, when there is almost no hydrophilic polymer present inside.
＜水洗い後ポリマー残留率＞
本形態に係る親水性ゴム成形体は、結合していない親水性ポリマー量が少ないことに加え、親水性ポリマーとプライマー層とが強く結合されているため、水洗いを行ってもポリマーの剥離が少ない。そのため、継続して使用しても所期の油汚れ落ち性を維持し得る。
<Polymer residual ratio after washing>
The hydrophilic rubber molded body according to this embodiment has a small amount of unbonded hydrophilic polymer, and since the hydrophilic polymer and the primer layer are strongly bonded, there is little peeling of the polymer even when washed with water. . Therefore, even if it is continuously used, the desired oil stain removal property can be maintained.
＜油汚れ落ち性＞
油汚れ落ち性の高さは、親水性や親油性を計測することで把握することが出来る。即ち、親油性が高い場合には、油汚れが表面から剥がれ難いため油汚れ落ち性が低く、親水性が高い場合には、油汚れの下に水が入り込み易いため油汚れ落ち性が高いと言える。本形態に係る親水性ゴム成形体は、前述のように、無機ケイ素結合が網状構造であることにより親水性ポリマーが広い範囲で結合している（換言すれば、多数の結合点にて結合している）ことから十分な親水性を有するため、高い油汚れ落ち性を有する。
<Oil stain removal>
The high oil stain removal property can be grasped by measuring hydrophilicity and lipophilicity. That is, when the lipophilicity is high, the oil stain is difficult to peel off from the surface, so the oil stain removal property is low, and when the hydrophilicity is high, water easily enters under the oil stain and the oil stain removal property is high. I can say that. As described above, in the hydrophilic rubber molded body according to this embodiment, the hydrophilic polymer is bonded in a wide range because the inorganic silicon bond is a network structure (in other words, bonded at a large number of bonding points). Therefore, it has a sufficient hydrophilicity and therefore has a high oil stain removal property.
≪親水性ゴム成形体の用途≫
本形態に係る親水性ゴム成形体は、水洗いすることで、当該親水性ゴム成形体上に付着した油汚れを除去可能であり、繰り返し水洗い可能であり、また水による膨潤が生じ難いという様々な機能を有する。従って、油汚れが生じ得る用途や使用後の洗浄が想定され得る用途等に対して好適に使用可能である。更には、水による膨潤が求められない用途に対して使用可能である。例えば、キッチン用品（スポンジや排水口のフタ）、建築材料、自動車・自転車周りの部材、下水用のカバー蓋用等である。
≪Use of hydrophilic rubber moldings≫
The hydrophilic rubber molded body according to this embodiment can be washed with water to remove oil stains adhering to the hydrophilic rubber molded body, can be repeatedly washed with water, and does not easily swell with water. It has a function. Therefore, it can be suitably used for applications where oil stains may occur or for cleaning that can be assumed after use. Furthermore, it can be used for applications where swelling with water is not required. For example, kitchen utensils (sponge and drain lid), building materials, automobile / bicycle components, sewage cover covers, and the like.
≪親水性ゴム成形体の準備≫
以下の手順に従って、実施例及び比較例に係る親水性ゴムを準備した。
＜実施例１＞
ゴム成形体として、５０×４０ｍｍ、厚み８ｍｍのＮＢＲラテックススポンジゴム（連続気泡体）を用意し、ジブチルエーテルを希釈剤とし、ポリシラザン（アクアミカ ＮＬ１２０Ａ、ＡＺ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ製）を５質量％濃度としたプライマー剤に、当該ラテックススポンジゴムを含侵した（表面処理工程）。その後、当該ラテックススポンジゴムを取り出し、遠心分離機にて、２０００ｒｐｍで１分間遠心分離することで余分なプライマーを取り除いた後、末端シラノール基を有するベタイン基含有親水性ポリマーＡ（大阪有機化学工業社製、ＬＡＭＢＩＣ−４００ＥＰ、重量平均分子量１５０００）を０．１質量％濃度に調整した親水化処理剤（希釈剤はエタノール）に当該ラテックススポンジゴムに含侵させ、８０℃１時間で反応させた（親水化工程）。親水性ポリマーＡのシラノール基と、ラテックススポンジゴムの表面に形成されたプライマー層表面とが、シランカップリング反応を起こし、親水性ポリマーＡがプライマー層に結合された実施例１に係る親水性ゴム成形体を得た。
＜実施例２＞
親水性ポリマーＡを２．００質量％濃度とした親水化処理剤を用いたこと以外は実施例１と同様の方法により、実施例２に係る親水性ゴム成形体を得た。
＜実施例３＞
親水性ポリマーＡを５．００質量％濃度とした親水化処理剤を用いたこと以外は実施例１と同様の方法により、実施例３に係る親水性ゴム成形体を得た。
＜実施例４＞
親水化処理剤として、水を希釈剤とし、親水性ポリマーＡの代わりに、末端シラノール基を有するベタイン基含有親水性ポリマーＢ（大阪有機化学工業社製、ＬＡＭＢＩＣ−５００ＷＰ）を用いたこと以外は実施例１と同様の方法により、実施例４に係る親水性ゴム成形体を得た。
＜実施例５＞
親水性ポリマーＢを２．００質量％濃度とした親水化処理剤を用いたこと以外は実施例４と同様の方法により、実施例５に係る親水性ゴム成形体を得た。
＜実施例６＞
親水性ポリマーＢを５．００質量％濃度とした親水化処理剤を用いたこと以外は実施例４と同様の方法により、実施例６に係る親水性ゴム成形体を得た。
＜実施例７＞
親水性ポリマーＢの代わりに、末端シラノール基を有するベタイン基含有親水性ポリマーＣ（大阪有機化学工業社製、ＬＡＭＢＩＣ−７７１Ｗ）を用いたこと以外は実施例４と同様の方法により、実施例７に係る親水性ゴム成形体を得た。
＜実施例８＞
親水性ポリマーＣを２．００質量％濃度とした親水化処理剤を用いたこと以外は実施例７と同様の方法により、実施例８に係る親水性ゴム成形体を得た。
＜実施例９＞
親水性ポリマーＣを５．００質量％濃度とした親水化処理剤を用いたこと以外は実施例７と同様の方法により、実施例９に係る親水性ゴム成形体を得た。
＜実施例１０＞
親水性ポリマーＡの代わりに、末端シラノール基を有するベタイン基含有親水性ポリマーＤ（大阪有機化学工業社製、ＴＲＡＰＩＳＴ−１００ＥＰ）を用いたこと以外は実施例１と同様の方法により、実施例１０に係る親水性ゴム成形体を得た。
＜実施例１１＞
親水性ポリマーＤを２．００質量％濃度とした親水化処理剤を用いたこと以外は実施例１０と同様の方法により、実施例１１に係る親水性ゴム成形体を得た。
＜実施例１２＞
親水性ポリマーＤを５．００質量％濃度とした親水化処理剤を用いたこと以外は実施例１０と同様の方法により、実施例１２に係る親水性ゴム成形体を得た。
＜実施例１３＞
ゴム成形体として、ＮＢＲソリッド（非発泡体）ゴムを用いたこと以外は、実施例１と同様の方法により、実施例１３に係る親水性ゴム成形体を得た。
＜実施例１４＞
親水性ポリマーＡを２．００質量％濃度とした親水化処理剤を用いたこと以外は実施例１３と同様の方法により、実施例１４に係る親水性ゴム成形体を得た。
＜実施例１５＞
親水性ポリマーＡを５．００質量％濃度とした親水化処理剤を用いたこと以外は実施例１３と同様の方法により、実施例１５に係る親水性ゴム成形体を得た。
＜比較例１＞
ゴム成形体として、５０×４０ｍｍ、厚み８ｍｍのＮＢＲラテックススポンジゴム（連続気泡体）を用意し、水を希釈剤とし、フッ素系処理剤Ａ（撥水撥油剤、旭化成社製、アサヒガードＡＧ−E０８２）を１質量％濃度とした処理剤に当該ラテックススポンジゴムを含侵させ、１００℃で１時間乾燥させた後、１５０℃で３分間キュアを行い、比較例１に係る親水性ゴム成形体を得た。
＜比較例２＞
フッ素系処理剤Ａを３質量％濃度とした処理剤を用いたこと以外は比較例１と同様の方法により、比較例２に係る親水性ゴム成形体を得た。
＜比較例３＞
フッ素系処理剤Ａを５質量％濃度とした処理剤を用いたこと以外は比較例１と同様の方法により、比較例３に係る親水性ゴム成形体を得た。
＜比較例４＞
処理剤として、フッ素処理剤Ｂ（フッ素高分子コーティング剤、ソルベイスペシャリティポリマーズ社製、Ｐ５６）を用いたこと以外は比較例１と同様の方法により、比較例４に係る親水性ゴム成形体を得た。
＜比較例５＞
フッ素系処理剤Ｂを３質量％濃度とした処理剤を用いたこと以外は比較例４と同様の方法により、比較例５に係る親水性ゴム成形体を得た。
＜比較例６＞
フッ素系処理剤Ｂを５質量％濃度とした処理剤を用いたこと以外は比較例４と同様の方法により、比較例６に係る親水性ゴム成形体を得た。
＜比較例７＞
実施例１３〜１５で用いた、親水化処理を施す前のソリッドゴムを、比較例７に係るゴム成形体とした。
≪Preparation of hydrophilic rubber molding≫
According to the following procedures, hydrophilic rubbers according to Examples and Comparative Examples were prepared.
<Example 1>
Primer with NBR latex sponge rubber (open cell) of 50 × 40 mm and thickness 8 mm prepared as rubber molding, dibutyl ether as diluent, polysilazane (Aquamica NL120A, manufactured by AZ Electronic Materials) at a concentration of 5% by mass The latex sponge rubber was impregnated in the agent (surface treatment step). Thereafter, the latex sponge rubber was taken out and centrifuged at 2000 rpm for 1 minute in a centrifuge to remove excess primer, and then a betaine group-containing hydrophilic polymer A having terminal silanol groups (Osaka Organic Chemical Co., Ltd.). Manufactured by LAMBIC-400EP, weight average molecular weight 15000) adjusted to 0.1% by mass with a hydrophilic treatment agent (diluent is ethanol) impregnated in the latex sponge rubber and reacted at 80 ° C. for 1 hour ( Hydrophilization process). The hydrophilic rubber according to Example 1 in which the silanol group of the hydrophilic polymer A and the surface of the primer layer formed on the surface of the latex sponge rubber cause a silane coupling reaction, and the hydrophilic polymer A is bonded to the primer layer. A molded body was obtained.
<Example 2>
A hydrophilic rubber molded body according to Example 2 was obtained in the same manner as in Example 1 except that a hydrophilic treatment agent having a hydrophilic polymer A concentration of 2.00% by mass was used.
<Example 3>
A hydrophilic rubber molded article according to Example 3 was obtained in the same manner as in Example 1 except that a hydrophilic treatment agent having a hydrophilic polymer A concentration of 5.00% by mass was used.
<Example 4>
As a hydrophilization treatment agent, water was used as a diluent, and a betaine group-containing hydrophilic polymer B having a terminal silanol group (LAMBIC-500WP, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used instead of the hydrophilic polymer A. A hydrophilic rubber molding according to Example 4 was obtained in the same manner as in Example 1.
<Example 5>
A hydrophilic rubber molded article according to Example 5 was obtained in the same manner as in Example 4 except that a hydrophilic treatment agent having a hydrophilic polymer B concentration of 2.00% by mass was used.
<Example 6>
A hydrophilic rubber molded body according to Example 6 was obtained in the same manner as in Example 4 except that a hydrophilic treatment agent having a hydrophilic polymer B concentration of 5.00% by mass was used.
<Example 7>
Example 7 was carried out in the same manner as in Example 4 except that betaine group-containing hydrophilic polymer C having a terminal silanol group (LAMBIC-771W, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used instead of hydrophilic polymer B. A hydrophilic rubber molded body according to the above was obtained.
<Example 8>
A hydrophilic rubber molded article according to Example 8 was obtained in the same manner as in Example 7, except that a hydrophilic treatment agent having a hydrophilic polymer C concentration of 2.00% by mass was used.
<Example 9>
A hydrophilic rubber molded article according to Example 9 was obtained in the same manner as in Example 7, except that a hydrophilic treatment agent having a hydrophilic polymer C concentration of 5.00% by mass was used.
<Example 10>
Example 10 was carried out in the same manner as Example 1 except that betaine group-containing hydrophilic polymer D having a terminal silanol group (TRAPIST-100EP, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used instead of hydrophilic polymer A. A hydrophilic rubber molded body according to the above was obtained.
<Example 11>
A hydrophilic rubber molded body according to Example 11 was obtained in the same manner as in Example 10 except that a hydrophilic treatment agent having a hydrophilic polymer D concentration of 2.00% by mass was used.
<Example 12>
A hydrophilic rubber molded body according to Example 12 was obtained in the same manner as in Example 10 except that a hydrophilic treatment agent having a hydrophilic polymer D concentration of 5.00% by mass was used.
<Example 13>
A hydrophilic rubber molded body according to Example 13 was obtained in the same manner as in Example 1 except that NBR solid (non-foamed) rubber was used as the rubber molded body.
<Example 14>
A hydrophilic rubber molded body according to Example 14 was obtained in the same manner as in Example 13, except that a hydrophilic treatment agent having a hydrophilic polymer A concentration of 2.00% by mass was used.
<Example 15>
A hydrophilic rubber molded body according to Example 15 was obtained in the same manner as in Example 13 except that a hydrophilic treatment agent having a hydrophilic polymer A concentration of 5.00% by mass was used.
<Comparative Example 1>
As a rubber molded body, NBR latex sponge rubber (open cell body) having a size of 50 × 40 mm and a thickness of 8 mm is prepared, and water is used as a diluent. Fluorine treatment agent A (water / oil repellent, Asahi Kasei Co., Ltd. The latex sponge rubber was impregnated in a treatment agent having a concentration of E082) of 1% by mass, dried at 100 ° C. for 1 hour, then cured at 150 ° C. for 3 minutes, and a hydrophilic rubber molded article according to Comparative Example 1 Got.
<Comparative example 2>
A hydrophilic rubber molded body according to Comparative Example 2 was obtained in the same manner as in Comparative Example 1 except that a treating agent having a fluorine-based treating agent A concentration of 3% by mass was used.
<Comparative Example 3>
A hydrophilic rubber molded body according to Comparative Example 3 was obtained in the same manner as in Comparative Example 1 except that a treating agent having a fluorine-based treating agent A concentration of 5% by mass was used.
<Comparative example 4>
A hydrophilic rubber molded article according to Comparative Example 4 is obtained by the same method as Comparative Example 1 except that Fluorine Treatment Agent B (Fluorine Polymer Coating Agent, Solvay Specialty Polymers, P56) is used as the treatment agent. It was.
<Comparative Example 5>
A hydrophilic rubber molded body according to Comparative Example 5 was obtained in the same manner as in Comparative Example 4 except that the treating agent having a fluorine-based treating agent B of 3% by mass was used.
<Comparative Example 6>
A hydrophilic rubber molded body according to Comparative Example 6 was obtained in the same manner as in Comparative Example 4 except that a treating agent having a fluorine-based treating agent B of 5% by mass was used.
<Comparative Example 7>
The solid rubber before the hydrophilization treatment used in Examples 13 to 15 was used as a rubber molded body according to Comparative Example 7.
≪評価試験≫
次に、準備した実施例及び比較例に係る親水性ゴム成形体を用いて評価試験を行った。
＜評価１＞膨潤率
実施例１〜１２及び比較例１〜６に係る親水性ゴム成形体に関して、水に浸漬させる前の試料体積と、浸漬後の試料体積との体積変化から、膨潤率を求めた。具体的には、試料片に対して過剰な程度の水雰囲気とし、試験片全体を浸漬させ、揉む等して内部まで水を含浸させた後に、一度乾燥させ、下記式（１）により膨潤率を求めた。その結果を表１〜３に示す。
膨潤率（％）＝（水浸漬後の体積）／（浸漬前の体積）×１００・・・（式１）
＜評価２＞水洗い後ポリマー残留率
実施例１〜１２及び比較例１〜６に係る親水性ゴム成形体に関して、水洗い後ポリマー残留率を求めた。具体的には、まず、試料の重量を測定し、次に、４０℃のお湯で３分間揉み洗いを行い（揉み洗い回数:１２０回／分）、乾燥させ、下記式（２）により水洗い後ポリマー残留率を求めた。その結果を表１〜３に示す。
水洗い後ポリマー残留率（％）＝（洗浄後のゴム成形体の重量）／（洗浄前のゴム成形体の重量）×１００・・・（式２）
＜評価３＞親水性、親油性及び汚れ落ち性
実施例１３〜１５及び比較例７に係るゴム成形体に関して、親水性、親油性及び汚れ落ち性を測定した。具体的には下記の通りである。
実施例１３〜１５及び比較例７に係るゴム成形体にサラダ油を一滴落とし、接触角を測定した（親油性試験）。その結果を表４及び図１に示す。当該試験においては、接触角が大きいほど、ソリッドゴム表面が親水性（疎油性）となっている。
実施例１３〜１５及び比較例７に係るゴム成形体に水を一滴落とし、基材との接触角を測定した（親水性試験）。その結果を表４及び図１に示す。当該試験においては、接触角が小さいほど、ソリッドゴム表面が親水性となっている。
実施例１３〜１５及び比較例７に係るゴム成形体にグリースを塗布し、当該試料を水中に1時間放置した後、軽く水を拭き取り表面を乾燥させる。さらに当該表面に水を一滴落とし、基材との接触角を測定した（汚れ落ち評価）。汚れ落ち評価方法の概要を図２に、評価試験結果を表４及び図１に示す。当該試験においては、接触角が小さいほど、グリースの汚れが落ちているといえる。
≪Evaluation test≫
Next, an evaluation test was performed using the prepared hydrophilic rubber molded bodies according to Examples and Comparative Examples.
<Evaluation 1> Swelling rate With respect to the hydrophilic rubber molded bodies according to Examples 1 to 12 and Comparative Examples 1 to 6, the swelling rate was determined from the volume change between the sample volume before being immersed in water and the sample volume after being immersed. Asked. Specifically, the water atmosphere is excessive with respect to the sample piece, the entire test piece is dipped, impregnated, etc., impregnated with water to the inside, and then dried once, and the swelling ratio is expressed by the following formula (1). Asked. The results are shown in Tables 1-3.
Swelling ratio (%) = (volume after water immersion) / (volume before immersion) × 100 (Equation 1)
<Evaluation 2> Polymer Residual Ratio After Washing With respect to the hydrophilic rubber molded bodies according to Examples 1 to 12 and Comparative Examples 1 to 6, the polymer residual ratio after washing with water was determined. Specifically, first, the weight of the sample is measured, and then it is rinsed with 40 ° C. hot water for 3 minutes (the number of massaging is 120 times / minute), dried, and washed with water according to the following formula (2). The polymer residual ratio was determined. The results are shown in Tables 1-3.
Polymer residual ratio after washing with water (%) = (weight of rubber molded body after cleaning) / (weight of rubber molded body before cleaning) × 100 (Equation 2)
<Evaluation 3> Hydrophilicity, lipophilicity, and stain removal properties With respect to the rubber molded bodies according to Examples 13 to 15 and Comparative Example 7, hydrophilicity, lipophilicity, and stain removal properties were measured. Specifically, it is as follows.
One drop of salad oil was dropped on the rubber molded bodies according to Examples 13 to 15 and Comparative Example 7, and the contact angle was measured (lipophilicity test). The results are shown in Table 4 and FIG. In the test, the larger the contact angle, the more hydrophilic (oleophobic) the solid rubber surface is.
A drop of water was dropped on the rubber molded bodies according to Examples 13 to 15 and Comparative Example 7, and the contact angle with the base material was measured (hydrophilicity test). The results are shown in Table 4 and FIG. In the test, the smaller the contact angle, the more hydrophilic the solid rubber surface.
Grease is applied to the rubber molded bodies according to Examples 13 to 15 and Comparative Example 7, and the sample is left in water for 1 hour, and then the surface is lightly wiped to dry the surface. Further, a drop of water was dropped on the surface, and the contact angle with the substrate was measured (soil removal evaluation). The outline of the dirt removal evaluation method is shown in FIG. 2, and the evaluation test results are shown in Table 4 and FIG. In the test, it can be said that the smaller the contact angle, the more grease is removed.
Claims (17)
ことを特徴とする親水性ゴム成形体。 Primer layer comprising a network-structured inorganic silicon compound having a siloxane bond represented by Si—O—Si or a silazane bond represented by Si—NH—Si as a skeleton, present on at least a part of the surface of a rubber molded body And a hydrophilic polymer are bonded via a siloxane bond.
親水性ポリマーを、シランカップリング反応により前記プライマー層の表面に結合させる親水化工程と
を含むことを特徴とする親水性ゴム成形体の製造方法。 Silazane represented by Si-O-Si or Si-NH-Si having a hydroxyl group on the surface by treating at least a part of the surface of the rubber foam with water glass or silazane. A surface treatment step of forming a primer layer comprising a network-structured inorganic silicon compound having a bond as a skeleton;
And a hydrophilic step of bonding a hydrophilic polymer to the surface of the primer layer by a silane coupling reaction.
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| WO2018155577A1 (en) * | 2017-02-27 | 2018-08-30 | リンテック株式会社 | Hydrophilic structure and production method for hydrophilic structure |
| CN116871149A (en) * | 2023-08-01 | 2023-10-13 | 深圳市亚微新材料有限公司 | Hydrophilic silica gel leather, manufacturing method and application of silazane in silica gel leather |
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