KR950702877A - Brittle oxide substrates strengthened by cross-linkable silanes - Google Patents

Brittle oxide substrates strengthened by cross-linkable silanes Download PDF

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KR950702877A
KR950702877A KR1019950700660A KR19950700660A KR950702877A KR 950702877 A KR950702877 A KR 950702877A KR 1019950700660 A KR1019950700660 A KR 1019950700660A KR 19950700660 A KR19950700660 A KR 19950700660A KR 950702877 A KR950702877 A KR 950702877A
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brittle oxide
coating
oxide support
silane
brittle
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KR1019950700660A
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윌리암 카슨 스티븐
데니스 파파누 빅터
리타드 더크스 리안
더글라스 콘라드 닐
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엘리자베스 엘. 맥더모트
엘프 아토켐 노쓰 아메리카, 인코포레이티드(Elf Atochem North America, Inc.)
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Publication of KR950702877A publication Critical patent/KR950702877A/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Paints Or Removers (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
  • Inorganic Insulating Materials (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Liquid Crystal (AREA)
  • Silicon Polymers (AREA)

Abstract

본 발명은, 취성 산화물 지지체를 실란계 조성물을 함유하는 수용액으로 피복시키는 단계 및 수득된 피막을 경화시켜 취성 산화물 지지체 위에 투명 층을 형성시키는 단계를 포함하여 취성 산화물 지지체의 강도를 강화시키거나 회복시키는 방법에 관한 것이다. 또한, 본 발명은 취성 산화물 지지체를 피복시키는데 사용되는 신규한 조성물 및 실란 피복된 취성 산화물 용기에 관한 것이다.The present invention includes the steps of coating a brittle oxide support with an aqueous solution containing a silane-based composition and curing the resulting film to form a transparent layer on the brittle oxide support to enhance or restore the strength of the brittle oxide support. It is about a method. The present invention also relates to novel compositions and silane coated brittle oxide containers used to coat brittle oxide supports.

Description

가교결합성 실란에 의해 강화된 취성 산화물 지지체(Brittle oxide substrates strengthened by cross-linkable silanes)Brittle oxide substrates strengthened by cross-linkable silanes

본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음Since this is an open matter, no full text was included.

Claims (48)

a) 취성 산화물 지지체를 사실상 유기 용매의 부재하에, 수용액 속에서 가수분해시 일반식(Ⅰ)을 갖은 실란계 조성물을 함유하는 수용액으로 피복시키는 단계 및 b) 수득된 피막을 경화시켜 취성 산화물 지지체 위에 투명 층을 형성시키는 단계를 포함하여, 취성 산화물 지지체를 강화시키는 방법.a) coating the brittle oxide support with an aqueous solution containing a silane-based composition having the general formula (I) upon hydrolysis in an aqueous solution, substantially in the absence of an organic solvent, and b) curing the resulting film on the brittle oxide support. Forming a transparent layer, the method of strengthening the brittle oxide support. (OH)3SiR″ (I)(OH) 3 SiR ″ (I) 상기식에서, R″는 유기 작용성 그룹이고, (i) 경화된 피막을 갖는 취성 산화물 지지체의 강도가 피복단계 전의 취성 산화물 지지체의 강도에 비하여 사실상 향상되도록 선택되고 (ii) 경화된 피막이 취성 산화물 지지체의 표지 부착성을 손상시키지 않도록 선택된다.Wherein R ″ is an organic functional group and is selected such that (i) the strength of the brittle oxide support having the cured coating is substantially improved relative to the strength of the brittle oxide support before the coating step and (ii) the cured coating is a brittle oxide support. It is selected so as not to impair the label adhesion of the. 제1항에 있어서, R″가 글리시독시프로필, 2-(3,4-에폭시사이클로헥실)에틸, 3,3-디메독시프로필, 3-우레이도프로필, 이들의 가수분해된 형태 및 이들의 혼합물로 이루어진 그룹으로부터 선택되는 방법.The compound of claim 1, wherein R ″ is glycidoxypropyl, 2- (3,4-epoxycyclohexyl) ethyl, 3,3-dimedoxypropyl, 3-ureidopropyl, hydrolyzed forms thereof and their Selected from the group consisting of a mixture of; 제1항에 있어서, 유기 작용성 그룹이 가수분해 가능한 실란인 방법.The method of claim 1 wherein the organic functional group is a hydrolyzable silane. 제1항에 있어서, 취성 산화물 지지체의 표지 부착성이 라벨 박리시험으로 측정하여 약 50% 이상인 방법.The method of claim 1 wherein the label adhesion of the brittle oxide support is at least about 50% as measured by a label peel test. 제1항에 있어서, 취성 산화물 지지체의 표지 부착성이 라벨 박리시험으로 측정하여 약 60% 이상인 방법.The method of claim 1, wherein the label adhesion of the brittle oxide support is at least about 60% as measured by a label peel test. 제1항에 있어서, 취성 산화물이 유리인 방법.The method of claim 1 wherein the brittle oxide is glass. 제1항에 있어서, 실란계 조성물이, 경화되는 경우, 취성 산화물과 화학적으로 반응하는 방법.The method of claim 1, wherein the silane-based composition reacts chemically with the brittle oxide when cured. 제1항에 있어서, 실란계 조성물이 윤활제, 염료, 형광제 및/또는 자외선 차단제로 이루어진 그룹으로부터 선택된 물질 하나 이상을 추가로 포함하는 방법.The method of claim 1, wherein the silane-based composition further comprises one or more materials selected from the group consisting of lubricants, dyes, fluorescent agents, and / or sunscreens. 제1항에 있어서, 단계(a)를 수행하기 전에, 취성 산화물 지지체에 금속 산화물 층을 도포하는 단계를 추가로 포함하는 방법.The method of claim 1, further comprising applying a metal oxide layer to the brittle oxide support prior to performing step (a). a) 취성 산화물 지지체를 사실상 용매의 부재하에, 수용액 속에서 가수분해시 일반식(Ⅰ)를 갖는 실란계 조성물을 함유하는 수용액으로 피복시키는 단계 및 b) 수득된 피막을 경화시켜 취성 산화물 지지체 위에 투명층을 형성시키는 단계를 포함하여, 취성 산화물 지지체를 강화시키는 방법.a) coating the brittle oxide support with an aqueous solution containing a silane-based composition having the general formula (I) upon hydrolysis in an aqueous solution, substantially in the absence of a solvent, and b) curing the obtained film to a transparent layer on the brittle oxide support. Forming a brittle oxide support. (OH)3SiR″ (I)(OH) 3 SiR ″ (I) 상기식에서, R″는 (i) 경화된 피막을 갖는 취성 산화물 지지체의 강도가 피복 단계 전의 취성 산화물 지지체의 강도에 비하여 사실상 향상되도록 선택되고 (ii) 취성 산화물 지지체 위의 경화된 피막으로부터 사실상 향상된 강도가 약 50% 이상의 유지된 내습성을 갖도록 선택된다.Wherein R ″ is selected such that (i) the strength of the brittle oxide support with the cured coating is substantially improved relative to the strength of the brittle oxide support before the coating step and (ii) the strength substantially improved from the cured coating on the brittle oxide support. Is selected to have a retained moisture resistance of at least about 50%. 제10항에 있어서, R″가 비닐 또는 메틸인 방법.The method of claim 10, wherein R ″ is vinyl or methyl. 제10항에 있어서, 취성 산화물이 유리인 방법.The method of claim 10, wherein the brittle oxide is glass. 제10항에 있어서, 실란계 조성물이, 경화되는 경우, 취성 산화물 지지체와 화학적으로 반응하는 방법.The method of claim 10 wherein the silane-based composition, when cured, reacts chemically with the brittle oxide support. 제10항에 있어서, 실란계 조성물이 윤활제, 염료, 형광제 및/또는 자외선 차단제로 이루어진 그룹으로부터 선택된 하나 이상의 물질을 추가로 포함하는 방법.The method of claim 10, wherein the silane-based composition further comprises one or more materials selected from the group consisting of lubricants, dyes, fluorescent agents, and / or sunscreens. 제10항에 있어서, 단계(a)를 수행하기 전에, 금속 산화물층을 취성 산화물 지지체에 도포하는 단계를 추가로 포함하는 방법.The method of claim 10, further comprising applying a metal oxide layer to the brittle oxide support prior to performing step (a). 제10항에 있어서, 유기 작용성 그룹이 가수분해 가능한 실란인 방법.The method of claim 10, wherein the organic functional group is a hydrolyzable silane. a) 유리 용기의 표면을 사실상 유기 용매의 부재하에, 수용액 속에서 가수분해시 일반식(Ⅰ)을 갖는 실란계 조성물을 함유하는 수용액으로 피복시키는 단계 및 b) 수득된 피막을 경화시켜 유리 용기의 표면에 투명 층을 형성시키는 단계를 포함하여, 유리 용기를 강화시키는 방법.a) coating the surface of the glass vessel with an aqueous solution containing a silane-based composition having formula (I) upon hydrolysis in an aqueous solution, substantially in the absence of an organic solvent, and b) curing the resulting coating to Forming a transparent layer on the surface. (OH)3SiR″ (I)(OH) 3 SiR ″ (I) 상기식에서, R″는 유기 작용성 그룹이고, (i) 경화된 피막을 갖는 유리 용기의 강도가 피복 단계를 수행하기 전의 유리 용기의 강도에 비하여 사실상 향상되도록 선택되고 (ii) 경화된 피막이 유리 용기의 외면의 표지 부착성을 손상시키지 않도록 선택된다.Wherein R ″ is an organic functional group and is selected such that (i) the strength of the glass container with the cured coating is substantially improved relative to the strength of the glass container prior to performing the coating step and (ii) the cured coating is a glass container It is selected so as not to impair the label adhesiveness of the outer surface of the. 제17항에 있어서, 유기 작용성 그룹이 가수분해 가능한 실란의 잔기인 방법.The method of claim 17, wherein the organic functional group is a residue of a hydrolyzable silane. 제17항에 있어서, R″가 글리시독시프로필, 2-(3,4-에폭시사이클로헥실)에틸, 3,3-디메독시프로필, 3-우레이도프로필, 이들의 가수분해된 형태 및 이들의 혼합물로 이루어진 그룹으로부터 선택되는 방법.18. The composition of claim 17, wherein R " is glycidoxypropyl, 2- (3,4-epoxycyclohexyl) ethyl, 3,3-dimedoxypropyl, 3-ureidopropyl, hydrolyzed forms thereof and their Selected from the group consisting of a mixture of; 제17항에 있어서, 취성 산화물 지지체의 표지 부착성이 라벨 박리시험으로 측정하여 약 50% 이상인 방법.The method of claim 17, wherein the label adhesion of the brittle oxide support is at least about 50% as measured by a label peel test. 제17항에 있어서, 취성 산화물 지지체의 표지 부착성이 라벨 박리시험으로 측정하여 약 60% 이상인 방법.The method of claim 17, wherein the label adhesion of the brittle oxide support is at least about 60% as measured by a label peel test. 제17항에 있어서, 실란계 조성물의 pH가 1.5 내지 11인 방법.18. The method of claim 17, wherein the pH of the silane based composition is between 1.5 and 11. 제17항에 있어서, 실란계 조성물의 수용액 중에서 1 내지 99%의 농도 범위로 존재하는 방법.18. The method of claim 17, wherein the solution is present in an aqueous solution of the silane composition in a concentration range of 1 to 99%. 제17항에있어서, 실란계 조성물이 2-(3,4-에폭시사이클로헥실)에틸 트리메톡시실란, 계면활성제 및 산성 수의 혼합물인 방법.18. The method of claim 17, wherein the silane based composition is a mixture of 2- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, surfactant and acidic water. 제17항에 있어서, 피복되지 않은 유리 용기의 강도가 파손 압력 시험으로 측정하여 10 내지 600psi의 범위의 방법.18. The method of claim 17, wherein the strength of the uncoated glass container is in the range of 10 to 600 psi as measured by the break pressure test. 제17항에 있어서, 유리 용기의 벽 두께가 0.1 내지 6mm의 범위인 방법.The method of claim 17, wherein the wall thickness of the glass container is in the range of 0.1 to 6 mm. (a) 취성 산화물 용기 및 (b) 취성 산화물 용기의 표면에 경화된 중합되어 가교 결합된 실록산의 투명 층(여기서, 중합되어 가교결합된 실록산은 사실상 유기 용매가 존재하지 않는 수성 실란계 조성물로부터 형성되고 MPTMO, GPTMO, VTMO, CETMO, MTMO, DMPTMO, 3-우레이도프로필트리메톡시실란, 1,2-비스(트리메톡시실릴)에탄, 1,2-비스(30트리메톡시실릴프로폭시)에탄, 5,6-에폭시헥실트리메톡시실란, N-(트리메톡시실릴프로필)말레산 아미드, 이들의 가수분해된 형태 및 이들의 혼합물로 이루어진 그룹으로부터 선택된다)을 포함하는 실란 피복된 취성 산화물 용기.A transparent layer of cured polymerized crosslinked siloxane on the surface of (a) brittle oxide container and (b) brittle oxide container, wherein the polymerized crosslinked siloxane is formed from an aqueous silane-based composition that is virtually free of organic solvents. MPTMO, GPTMO, VTMO, CETMO, MTMO, DMPTMO, 3-ureidopropyltrimethoxysilane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (30trimethoxysilylpropoxy) Silane coated brittles including ethane, 5,6-epoxyhexyltrimethoxysilane, N- (trimethoxysilylpropyl) maleic acid amide, hydrolyzed forms thereof, and mixtures thereof) Oxide containers. 제27항에 있어서, 유리병인 용기.The container of claim 27 which is a glass bottle. 제28항에 있어서, 유리병의 벽 두께가 0.1 내지 6mm의 범위인 용기.29. The container of claim 28, wherein the wall thickness of the vial is in the range of 0.1 to 6 mm. 제27항에 있어서, 중합되어 가교결합된 실록산의 투명층의 표면에 라벨을 포함하는 용기.The container of claim 27, comprising a label on the surface of the transparent layer of polymerized crosslinked siloxane. 제30항에 있어서, 표면의 표지 부착성이 라벨 박리시험으로 측정하여 약 60% 이상인 용기.31. The container of claim 30, wherein the label adhesion of the surface is at least about 60% as measured by a label peel test. 제27항에 있어서, 중합되어 가교결합된 실록산의 투명층과 용기의 외면 사이에 금속 산화물 층을 추가로 포함하는 용기.The container of claim 27, further comprising a metal oxide layer between the transparent layer of polymerized crosslinked siloxane and the outer surface of the container. 제27항에 있어서, 중합되어 가교결합된 실록산층의 표면에 윤활제 피막을 추가로 포함하는 용기.28. The container of claim 27, further comprising a lubricant coating on the surface of the polymerized crosslinked siloxane layer. 제33항에 있어서, 윤활제 피막의 표면에 라벨을 추가로 포함하는 용기.34. The container of claim 33, further comprising a label on the surface of the lubricant coating. 제1항에 있어서, 실란계 조성물이 MPTMO와 가수분해된 CETMO의 혼합물; MTMO, 가수분해된 CETMO 및 가수분해된 GPTMO의 혼합물; 가수분해된 CETMO와 가수분해된 CPTMO의 혼합물; VTMO와 가수분해된 CETMO의 혼합물 또는 가수분해된 DMPTMO와 가수분해된 CETMO의 혼합물인 방법.The composition of claim 1, wherein the silane based composition comprises a mixture of MPTMO and hydrolyzed CETMO; A mixture of MTMO, hydrolyzed CETMO and hydrolyzed GPTMO; A mixture of hydrolyzed CETMO and hydrolyzed CPTMO; A mixture of VTMO and hydrolyzed CETMO or a mixture of hydrolyzed DMPTMO and hydrolyzed CETMO. a) 취성 산화물 지지체를 사실상 유기 용매의 부재하에, 수용액 속에서 가수분해시 일반식(Ⅰ)을 갖는 실란계 조성물을 함유하는 수용액으로 피복시키는 단계 및 b) 수득된 피막을 경화시켜 취성 산화물 지지체 위에 투명 층을 형성시키는 단계를 포함하여, 취성 산화물 지지체의 강도를 회복하는 방법.a) coating the brittle oxide support with an aqueous solution containing a silane-based composition having the general formula (I) upon hydrolysis in an aqueous solution, substantially in the absence of an organic solvent, and b) curing the resulting film on the brittle oxide support. Forming a transparent layer to restore the strength of the brittle oxide support. (OH)3SiR″ (I)(OH) 3 SiR ″ (I) 상기식에서, R″는 유기 작용성 그룹이고, (i) 경화된 피막을 갖는 취성 산화물 지지체의 강도가 피복 단계를 수행하기 전에 취성 산화물 지지체의 강도에 비하여 사실상 향상되도록 선택되고 (ii) 경화된 피막이 취성 산화물 지지체의 표지 부착물을 손상시키지 않도록 선택된다.Wherein R ″ is an organic functional group and is selected such that (i) the strength of the brittle oxide support having the cured coating is substantially improved relative to the strength of the brittle oxide support before carrying out the coating step and (ii) the cured coating is It is selected so as not to damage the label attachment of the brittle oxide support. a) 장력을 지닌 표면을 사실상 유기 용매의 부재하에, 수용액 속에서 가수분해시 일반식(Ⅰ)을 갖는 실란계 조성물로 피복시키는 단계 및 b) 수득된 피막을 경화시켜 장력을 지닌 투명 층을 형성시키는 단계를 포함하여, 장력을 지닌 표면의 결합을 부분적으로 또는 완전하게 처리하는 방법.a) coating the tensioned surface with an silane-based composition having the general formula (I) upon hydrolysis in aqueous solution, substantially in the absence of an organic solvent, and b) curing the obtained film to form a transparent transparent layer with tension. And partially or completely treating the bonding of the tensioned surface, including the step of making it. (OH)3SiR″ (I)(OH) 3 SiR ″ (I) 상기식에서, R″는 유기 작용성 그룹이고, (i) 경화된 피막을 갖는 장력을 지닌 표면의 강도가 피복 단계를 수행하기 전의 장력을 지닌 표면의 강도에 비하여 사실상 향상되도록 선택되고 (ii) 경화된 피막이 장력을 지닌 표면의 표지 부착성을 손상시키지 않도록 선택된다.Wherein R ″ is an organic functional group and is selected such that (i) the strength of the tensioned surface with the cured coating is substantially improved relative to the strength of the tensioned surface prior to performing the coating step and (ii) curing The coated film is selected so as not to impair the label adhesion of the tensioned surface. 제37항에 있어서, 장력을 지닌 표면이 취성 산화물 지지체인 방법.38. The method of claim 37, wherein the tensioned surface is a brittle oxide support. 제37항에 있어서, 장력을 지닌 표면이 유리 용기인 방법.38. The method of claim 37, wherein the tensioned surface is a glass container. CETMO와 VTMO의 혼합물을 함유하는 취성 산화물 지지체의 피복용으로 유용간 조성물.A useful composition for coating a brittle oxide support containing a mixture of CETMO and VTMO. CETMO와 MTMO의 혼합물을 함유하는 취성 산화물 지지체의 피복용으로 유용한 조성물.A composition useful for coating a brittle oxide support containing a mixture of CETMO and MTMO. GPTMO, CETMO 및 MTMO의 혼합물을 함유하는 취성 산화물 지지체의 피복용으로 유용한 조성물.Compositions useful for coating brittle oxide supports containing a mixture of GPTMO, CETMO and MTMO. GPTMO와 CETMO의 혼합물을 함유하는 취성 산화물 지지체의 피복용으로 유용한 조성물.Compositions useful for coating brittle oxide supports containing mixtures of GPTMO and CETMO. UPTMO를 함유하는 취성 산화물 지지체의 피복용으로 유용한 조성물.Compositions useful for coating brittle oxide supports containing UPTMO. 1, 2-비스(트리메톡시실릴)에탄을 함유하는 취성 산화물 지지체의 피복용으로 유용한 조성물.Compositions useful for coating brittle oxide supports containing 1, 2-bis (trimethoxysilyl) ethane. 1, 2-비스(3-트리메톡시실릴프로폭시)에탄을 함유하는 취성 산화물 지지체의 피복용으로 유용한 조성물.A composition useful for coating a brittle oxide support containing 1, 2-bis (3-trimethoxysilylpropoxy) ethane. GMPTMO와 CETMO의 혼합물을 함유하는 취성 산화물 지지체의 피복용으로 유용한 조성물.Compositions useful for coating brittle oxide supports containing a mixture of GMPTMO and CETMO. 제1항에 있어서, 실란계 조성물을 약 80℃ 내지 약 100℃의 온도에서 취성 산화물 지지체에 도포시킴으로써, 경화되는 경우, 확산된 외관을 생성하도록 하는 방법.The method of claim 1, wherein the silane-based composition is applied to the brittle oxide support at a temperature of about 80 ° C. to about 100 ° C. to produce a diffused appearance when cured. ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.※ Note: The disclosure is based on the initial application.
KR1019950700660A 1993-06-21 1994-06-21 Brittle oxide substrates strengthened by cross-linkable silanes KR950702877A (en)

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