CN1694937A - 硫化型粘合剂组合物 - Google Patents

硫化型粘合剂组合物 Download PDF

Info

Publication number
CN1694937A
CN1694937A CNA038247003A CN03824700A CN1694937A CN 1694937 A CN1694937 A CN 1694937A CN A038247003 A CNA038247003 A CN A038247003A CN 03824700 A CN03824700 A CN 03824700A CN 1694937 A CN1694937 A CN 1694937A
Authority
CN
China
Prior art keywords
adhesive composition
weight part
rubber
nitrile
sulfur
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.)
Granted
Application number
CNA038247003A
Other languages
English (en)
Other versions
CN1326965C (zh
Inventor
深泽清文
贝濑友宏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nok Corp
Original Assignee
Nok Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nok Corp filed Critical Nok Corp
Publication of CN1694937A publication Critical patent/CN1694937A/zh
Application granted granted Critical
Publication of CN1326965C publication Critical patent/CN1326965C/zh
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/02—Copolymers with acrylonitrile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/06—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • C09J123/28—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C09J123/286—Chlorinated polyethylene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
    • C09J165/04—Polyxylylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C08L23/286—Chlorinated polyethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C08L2666/06—Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/12—Homopolymers or copolymers not provided for in C08L2666/06 - C08L2666/10
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/16—Addition or condensation polymers of aldehydes or ketones according to C08L59/00 - C08L61/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/22—Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C08L65/04—Polyxylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31688—Next to aldehyde or ketone condensation product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y10T428/31696—Including polyene monomers [e.g., butadiene, etc.]

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

一种硫化型粘合剂组合物，包含100重量份酚亚二甲苯基树脂或酚联苯树脂、10～1,000重量份甲阶酚醛树脂型酚树脂、0～1,000重量份线型酚醛清漆型酚树脂、10～1,000重量份未硫化丁腈橡胶和10～500重量份氯化聚乙烯，能有效涂布在腈含量18～48％的(氢化)丁腈橡胶上，即使将其长期暴露直至浸在诸如flon气体、聚亚烷基二醇、水等各种低温液体中也具有对粘性降低的抑制作用。

Description

硫化型粘合剂组合物
技术领域
本发明涉及一种硫化型粘合剂组合物，更具体地说，涉及一种可有效应用于金属和(氢化)丁腈橡胶之间硫化粘合的硫化型粘合剂组合物。
背景技术
在金属和丁腈橡胶(NBR)之间的粘合中，应用氯化橡胶系列或线型酚醛清漆型酚树脂系列粘合剂。氯化橡胶系列粘合剂不能与金属粘合，所以必须预先向那里使用酚系列底胶。另外，由于这种底胶粘度高，所以其可用性也差。为了获得更好的粘合，底胶薄膜的厚度必须至少为5μm，这样，在尺寸要求精确的零件或配合零件等情况下就会产生麻烦。在另一方面，线型酚醛清漆型酚树脂系列粘合剂仅可对腈含量30～40％的(氢化)NBR实施粘合，因此，可用橡胶范围有限，还有粘合剂含有六亚甲基二胺固化剂，这样在干燥和烘烤期间就会产生麻烦以致于污染干燥器内侧。另外，所有这些粘合剂对各种低温液体如氟隆(flon)气体、水、PAG(聚亚烷基二醇)等的耐受性低，这样在应用于低温液体密封时就会产生困难。
为了解决这些问题，本申请人以前提出过一种包含甲阶酚醛树脂型酚树脂、未硫化的NBR、氯化聚乙烯等基本组分的硫化型粘合剂组合物(JP-A-6-306340和JP-A-8-302323)。虽然所提出的硫化型粘合剂组合物能够向腈含量为30％以下的(氢化)NBR赋予良好的粘合性，但是仍没有对腈含量为40％或更高的(氢化)NBR显示良好粘合性，还有，虽然与上述氯化橡胶系列或酚醛树脂系列粘合剂相比，对各种低温液体的耐受性较好，但是仍然没有满足现在的技术要求水平。
发明内容
本发明的目的是提供一种应用于金属和(氢化)丁腈橡胶之间硫化粘合的硫化型粘合剂组合物，其可有效应用于腈含量为18～48％的(氢化)丁腈橡胶，并且，即使将其长期浸渍在诸如氟隆(flon)气体、聚亚烷基二醇和水等各种低温液体中，其粘合性能够得到保持而不降低。
本发明的目的能够通过一种硫化型粘合剂组合物而实现，其包含100重量份酚亚二甲苯基树脂或酚联苯树脂、10～1,000重量份甲阶酚醛树脂型酚树脂、0～1,000重量份线型酚醛清漆型酚树脂、10～1,000重量份未硫化丁腈橡胶和10～500重量份氯化聚乙烯。
酚亚二甲苯基树脂是1，4-二(烷氧基甲基)苯和苯酚或在苯酚的2，4-位含有至少一个羟甲基基团的苯酚衍生物的缩聚产物，它实际上是一种市售产品，例如，MR-7800等，Meiwa Kasei公司的产品，能够以其本身应用于本发明。酚联苯树脂是4，4’-二(烷氧基甲基)联苯和苯酚或在苯酚的2，4-位含有至少一个羟甲基基团的苯酚衍生物的缩聚产物，它实际上是一种市售产品，例如，MR-7850等，Meiwa Kasei公司的产品，能够以其本身应用于本发明。
应用于本发明的酚树脂是甲阶酚醛树脂型酚树脂或者连同线型酚醛清漆型酚树脂使用。为此目的使用的甲阶酚醛树脂型酚树脂是通过在碱性催化剂存在下酚类和甲醛进行缩合反应所得的产物。用于缩合反应的酚包括在相对于苯酚、对甲酚、间甲酚和对叔丁基酚等的酚羟基的邻和/或对位具有两个或三个可置换的环上氢原子的酚，以及其混合物。为此目的使用的碱性催化剂包括氨、碱金属氢氧化物、氢氧化镁等。优选使用自间甲酚和对甲酚的混合物和甲醛生产的甲阶酚醛树脂型酚树脂。
为此目的使用的线型酚醛清漆型酚树脂是通过在酸性催化剂存在下酚类和甲醛进行缩合反应得到的产物。在缩合反应中使用的酚包括在相对于苯酚、对甲酚、间甲酚和对叔丁基酚等的酚羟基的邻和/或对位具有两个或三个可置换的环上氢原子的酚，以及其混合物。为此目的应用的酸性催化剂包括草酸、氢氯酸和马来酸等。
用于本发明的未硫化丁腈橡胶是任何一种市场可得的各种丁腈橡胶，包括下述腈含量者，极高腈含量(腈含量：43％或更高)，高腈含量(腈含量：36～42％)，中高腈含量(腈含量：31～35％)，中腈含量(腈含量：25～30％)，和低腈含量(腈含量：24％或更低)。优选具有中高腈含量的丁腈橡胶。
用于本发明的氯化聚乙烯优选为氯含量为约60～约70％的高氯化型者。
在本发明中，上述组分按照以下比例应用，以100重量份酚亚二甲苯基树脂或酚联苯树脂为基准计：
甲阶酚醛树脂型酚树脂：约10～约1,000重量份，优选约20～约400
                    重量份
线型酚醛清漆型酚树脂：0～1,000重量份，优选0～100重量份
未硫化丁腈橡胶：10～1,000重量份，优选20～300重量份
氯化聚乙烯：10～500重量份，优选10～200重量份
在甲阶酚醛树脂型酚树脂或者所述树脂和线型酚醛清漆型酚树脂的比例为约1,000重量份以上时，对氟隆(flon)或水的粘合耐久性下降，而当甲阶酚醛树脂型酚树脂的比例为约10重量份以下时，与金属的初始粘合性下降。当未硫化丁腈橡胶的应用比例为1,000重量份以上时，与金属的粘合性下降，和，粘度增加很多，使涂布施工困难，而比例为10重量份以下时，与粘合对应物丁腈橡胶的相容性下降，结果粘合失败。在氯化聚乙烯比例为500重量份以上时，粘合层变脆，导致强度下降，而比例为10重量份以下时，与橡胶的反应性下降，致使粘合性变差。
包含作为基本组分的这些组分的硫化型粘合剂组合物能够按照下述方法以液态制备：将所述各组分溶解在单一有机溶剂中，例如酮(如甲乙酮、甲基·异丁基酮等)或者芳烃(如甲苯、二甲苯等)或者其混合物，使固体含量为3～10wt％。
包含上述组分的本发明硫化型粘合剂组合物的硫化粘合按照下述方法实施，将本硫化型粘合剂组合物涂布到金属上如低碳钢、不锈钢、铝、模铸铝、黄铜、锌等，一般涂布到金属板上，然后在室温下空气干燥和在约100℃至约200℃下干燥约5～约30min，再使未硫化混炼(氢化)丁腈胶与其接触，此后在约150℃至约200℃下加压硫化，即，在(氢化)丁腈橡胶的硫化温度下进行。
具体实施方式
下文参见实施例叙述本发明，其中数量均以重量份表示，括弧内的量为固体物质的重量份。
实施例1
酚亚二甲苯基树脂(MR-7800，Meiwa Kasei公司         143(100)的产品，固体含量：70％)
甲阶酚醛树脂型酚树脂(AF-2639 L，Dainippon Ink      67(40)& Chemicals公司的产品，固体含量：60％)
未硫化丁腈橡胶(N-237，Japan Synthetic Rubber       40公司的产品)
氯化聚乙烯(Z-200，Daiso公司的产品，氯含量：        2067％)
甲乙酮                                             1865
甲苯                                               1865
实施例2
酚亚二甲苯基树脂(MR-7800)                          143(100)
甲酚改性的线型酚醛清漆型酚树脂(KA-1053L，          20(8)Dainippon Ink & Chemicals公司的产品，固体含量：40％)
甲阶酚醛树脂型酚树脂(AF-2639L)                      53(32)
未硫化丁腈橡胶(N-237)                               40
氯化聚乙烯(Z-200)                                   20
甲乙酮                                              1862
甲苯                                                1862
实施例3
酚联苯树脂(MR-7851，Meiwa Kasei公司产品，           143(100)固体含量：70％)
甲阶酚醛树脂型酚树脂(AF-2639L)                      67(40)
未硫化丁腈橡胶(N-237)                               40
氯化聚乙烯(Z-200)                                   20
甲乙酮                                              1865
甲苯                                                1865
实施例4
酚联苯树脂(MR-7851)                                 143(100)
甲酚改性的线型酚醛清漆型酚树脂(KA-1053L)            20(8)
甲阶酚醛树脂型酚树脂(AF-2639L)                      53(32)
未硫化丁腈橡胶(N-237)                          40
氯化聚乙烯(Z-200)                              20
甲乙酮                                         1862
甲苯                                           1862
比较例1
甲阶酚醛树脂型酚树脂(AF-2639L)                 167(100)
未硫化丁腈橡胶(N-237)                          28
氯化聚乙烯(Z-200)                              14
甲乙酮                                         916
甲苯                                           916
比较例2
甲阶酚醛树脂型酚树脂(AF-2639L)                 167(100)
甲酚线型酚醛清漆型环氧树脂(Epikron N695，      40
Dainippon Ink & Chemicals公司产品)
未硫化丁腈橡胶(N-237)                          40
氯化聚乙烯(Z-200)                              20
甲乙酮                                         1867
甲苯                                           1867
比较例3
甲酚改性的线型酚醛清漆型酚树脂(KA-1053L)       250(100)
甲阶酚醛树脂型酚树脂(AF-2639L)                 167(100)
未硫化丁腈橡胶(N-237)                          58
氯化聚乙烯(Z-200)                              29
甲乙酮                                         2618
甲苯                                           2618
比较例4
以氯化橡胶为基础的粘合剂(Chemlok 252X，Rhode Far East公司的产品)
将包含实施例1～4和比较例1～4的上述组分的各硫化型粘合剂组合物，分别涂布到磷酸锌处理过的低碳钢板上，经空气干燥同时在室温下搁置10min，然后在烘烤温度150℃下烘烤处理10min。
使下述组合物1～3的未硫化氢化丁腈橡胶混炼胶(单位：重量份)分别与烘烤过的硫化型粘合剂低碳钢板接触，和经180℃加压硫化6min。对所得硫化粘合产物进行初始粘合性试验、耐水性试验、耐PAG试验和耐flon试验。
初始粘合性试验：JIS K6256 90°剥离试验
耐水性试验：将JIS K6256 90°剥离试片浸在80℃热水中，和在浸后100hr进行剥离试验
耐PAG试验：将JIS K6256 90°剥离试片浸在150℃下PAG(聚亚烷基二醇)油中，和在浸后100hr进行剥离试验
耐Flon试验：将0.5mm厚橡胶片置于JIS K6256 90°剥离试验用的涂布粘合剂的金属板上经加压硫化模压制得试样，将所得试样置于加压容器中，将flon气体(R134a)注入所用容器中
在40℃环境下放置24hr之后，从容器中取出样品，在150℃烘箱中加热1hr对因氟隆(flon)气体而在粘合界面产生的发泡点进行计数
氢化丁腈橡胶组合物1～3
                                 组合物  组合物  组合物
                                  1        2        3
HNBR(Zetpol 2020，Nippon Zeon    100     100
公司产品，CN36％)
HNBR(Zetpol 1020，Nippon Zeon                    100
公司产品，CN44％)
N990碳黑                         10      140
SRF碳黑                                           51
白炭黑(比表面积70m2/g)           60
氧化锌                           5        5        5
硬脂酸                             0.5    0.5    0.5
基于二苯胺的抗氧剂(Nocrack CD，    1.5    1.5    0.5
Ouchi-Shinko Kagaku公司的产品)
基于咪唑的抗氧剂(Nocrack MB，      1.5    1.5    2
Ouchi-Shinko Kagaku公司产品)
1，3-二(叔丁基过氧异丙基)苯(含     10     10     10
量40％)  (Peroxymon F40，NOF公
司产品)
基于己二酸的增塑剂(RS107，Asahi    10     10     2
Denka Kogyo公司产品)
乙烯基硅烷化合物(A151，Nippon      2
Unicar公司产品)
加工助剂(Vestenemar 8012，Huels           5      5
公司产品)
结果列于下表1～3。
                     表1(混炼胶1)
                    实施例               比较例
                    1      2      3      4      1      2      3      4
[初始粘合试验]
粘合强度(N/mm)     18.8  18.8  18.6  18.9  8.8   6.5   18.8  18.9
橡胶保留百分率(％) 100   100   100   100   10    0     100   100
[耐水性试验]
粘合强度  (N/mm)   18.5  18.5  18.5  18.5   -     -    18.5  10.1
橡胶保留百分率(％) 100   100   100   100    -     -    100   0
[耐PAG试验]
粘合强度(N/mm)        17.5   17.5  17.5  17.5  -  -  17.5   16.5
橡胶保留百分率(％)    100    100   100   100   -  -  100    80
[耐Flon试验]
起泡点个数            0      0     0      0    -  -   6     20
                       表2(混炼胶2)
                       实施例                    比较例
                       1      2       3      4      1      2      3      4
[初始粘合试验]
粘合强度(N/mm)        17.9   18.1  17.9  17.8  17.8  17.7  17.9  17.9
橡胶保留百分率(％)    100    100   100   100   100   100   100   100
[耐水性试验]
粘合强度(N/mm)        17.5   17.3  17.1  17.3  11.1  17.1  17.5  8.5
橡胶保留百分率(％)    100    95    100   90    20    70    70    0
[耐PAG试验]
粘合强度(N/mm)        17.5   17.5  17.5  17.5  17.3  16.5  17.5  16.5
橡胶保留百分率(％)    100    100   100   100   100   90    100   70
[耐Flon试验]
起泡点个数            0      0     0     0     3     7     5     15
                   表3(混炼胶3)
                       实施例                   比较例
                       1      2      3      4      1      2      3      4
[初始粘合试验]
粘合强度(N/mm)        17.1  17.2  17.1  17.3  17.0  17.2  17.2  17.2
橡胶保留百分率(％)    100   100   100   100   100   100   100   100
[耐水性试验]
粘合强度(N/mm)        16.9  16.8  16.9  16.9   14.5  15.9  15   6.5
橡胶保留百分率(％)    100   100   100   100    50    80    60   0
[耐PAG试验]
粘合强度(N/mm)        17    16.8  16.9  16.9   16.4  16.9  16.9 12
橡胶保留百分率(％)    100   100   100   100    90    100   100  60
[耐Flon试验]
起泡点个数            0     0     0     0      1     3     6    10
工业应用
在金属和(氢化)丁腈橡胶的硫化粘合中，本硫化型粘合剂组合物能有效地施涂在腈含量18～48％的(氢化)丁腈橡胶上；即使将本组合物长期暴露在flon气体中或浸在聚亚烷基二醇或水中，其也具有对粘性降低的抑制作用。通过本硫化型粘合剂组合物彼此硫化粘合的金属和(氢化)丁腈橡胶构制的整体密封件能够有效地用作低温液体密封等。
权利要求书
(按照条约第19条的修改)
1.(修改为)一种硫化型粘合剂组合物，包含100重量份含有羟甲基基团的酚亚二甲苯基树脂，其为1，4-二(烷氧基甲基)苯和在2，4-位有至少一个羟甲基基团的酚的缩合产物，或者，100重量份含有羟甲基基团的酚联苯树脂，其为4，4’-二(烷氧基甲基)联苯和在2，4-位有至少一个羟甲基基团的酚的缩合产物，10～1,000重量份甲阶酚醛树脂型酚树脂，0～1,000重量份线型酚醛清漆型酚树脂，10～1,000重量份未硫化丁腈橡胶和10～500重量份氯化聚乙烯；该组合物用于金属和腈含量为18～48％的丁腈橡胶或氢化丁腈橡胶之间的硫化粘合。
2.按照权利要求1的硫化型粘合剂组合物，以有机溶剂溶液的形式制备。
3.(删去)
4.一种金属和丁腈橡胶或氢化丁腈橡胶构成的整体密封件，通过按照权利要求1或2的硫化型粘合剂组合物使彼此硫化粘合制成。
5.按照权利要求4的整体密封件用于低温液体密封。

Claims (5)

1.一种硫化型粘合剂组合物，包含100重量份酚亚二甲苯基树脂或酚联苯树脂、10～1,000重量份甲阶酚醛树脂型酚树脂、0～1,000重量份线型酚醛清漆型酚树脂、10～1,000重量份未硫化丁腈橡胶和10～500重量份氯化聚乙烯。
2.按照权利要求1的硫化型粘合剂组合物，以有机溶剂溶液的形式制备。
3.按照权利要求1或2的硫化型粘合剂组合物，用于金属和丁腈橡胶或氢化丁腈橡胶之间的硫化粘合。
4.一种由金属和丁腈橡胶或氢化丁腈橡胶构成的整体密封件，通过按照权利要求1或2的硫化型粘合剂组合物使彼此硫化粘合制成。
5.按照权利要求4的整体密封件，用于低温液体密封。
CNB038247003A 2003-08-27 2003-08-27 硫化型粘合剂组合物 Expired - Lifetime CN1326965C (zh)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2003/010829 WO2005023952A1 (ja) 2003-08-27 2003-08-27 加硫接着剤組成物

Publications (2)

Publication Number Publication Date
CN1694937A true CN1694937A (zh) 2005-11-09
CN1326965C CN1326965C (zh) 2007-07-18

Family

ID=34260066

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB038247003A Expired - Lifetime CN1326965C (zh) 2003-08-27 2003-08-27 硫化型粘合剂组合物

Country Status (5)

Country Link
US (1) US7247388B2 (zh)
EP (1) EP1659161B1 (zh)
CN (1) CN1326965C (zh)
AU (1) AU2003261749A1 (zh)
WO (1) WO2005023952A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104379695A (zh) * 2012-06-01 2015-02-25 株式会社Tkx 树脂结合线锯用的粘接剂组合物以及树脂结合线锯的制造方法
CN112175257A (zh) * 2020-07-27 2021-01-05 浙江中瑞橡胶高分子材料股份有限公司 一种发泡耐磨型橡胶

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9925741B2 (en) * 2007-06-06 2018-03-27 Nok Corporation Acrylic rubber-metal composite
JP6099535B2 (ja) * 2013-09-26 2017-03-22 住友理工株式会社 導電性ロールおよびその製造方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1195793A (en) * 1981-12-28 1985-10-22 Lester T. Toy Elastomer based adhesive compositions
JPH07107153B2 (ja) * 1987-05-26 1995-11-15 エヌオーケー株式会社 加硫接着剤配合物及びそれを用いる接着方法
JPH0791523B2 (ja) * 1987-12-25 1995-10-04 エヌオーケー株式会社 加硫接着剤配合物
JP2813642B2 (ja) 1992-07-14 1998-10-22 株式会社クボタ コンバインの伝動構造
JP3484743B2 (ja) * 1993-02-26 2004-01-06 Ｎｏｋ株式会社 接着剤組成物
JPH0748426A (ja) * 1993-05-31 1995-02-21 Mitsui Toatsu Chem Inc 固形熱硬化性レゾール樹脂、その製造方法およびその用途
CA2180338A1 (en) * 1994-01-18 1995-07-20 Richard J. Pokorny Pressure sensitive adhesive composition and products
JP3391148B2 (ja) * 1995-05-10 2003-03-31 エヌオーケー株式会社 加硫接着剤組成物
US6576394B1 (en) * 2000-06-16 2003-06-10 Clariant Finance (Bvi) Limited Negative-acting chemically amplified photoresist composition
JP4749621B2 (ja) * 2001-01-09 2011-08-17 三井化学株式会社 ノボラックアラルキル樹脂及びその製造方法、並びに該樹脂組成物
JP4085658B2 (ja) * 2002-03-08 2008-05-14 Ｎｏｋ株式会社 加硫接着剤組成物

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104379695A (zh) * 2012-06-01 2015-02-25 株式会社Tkx 树脂结合线锯用的粘接剂组合物以及树脂结合线锯的制造方法
CN104379695B (zh) * 2012-06-01 2016-08-17 株式会社Tkx 树脂结合线锯的制造方法
CN112175257A (zh) * 2020-07-27 2021-01-05 浙江中瑞橡胶高分子材料股份有限公司 一种发泡耐磨型橡胶
CN112175257B (zh) * 2020-07-27 2022-03-29 浙江中瑞橡胶高分子材料股份有限公司 一种发泡耐磨型橡胶

Also Published As

Publication number Publication date
US20050215712A1 (en) 2005-09-29
EP1659161A1 (en) 2006-05-24
AU2003261749A1 (en) 2005-03-29
WO2005023952A1 (ja) 2005-03-17
US7247388B2 (en) 2007-07-24
EP1659161B1 (en) 2011-11-23
CN1326965C (zh) 2007-07-18
EP1659161A4 (en) 2009-01-21

Similar Documents

Publication Publication Date Title
US8641047B2 (en) Fluororubber-metal laminate gasket material
JP5011886B2 (ja) ボンデッドピストンシール
CN1060101A (zh) 酚醛树脂粘合促进剂以及粘合剂组合物
CN1659028A (zh) 含有氟化聚合物层的多层制品粘合和粘结
CN1531569A (zh) 含氟聚合物与基材粘合的方法以及由此得到的复合制品
JP4483610B2 (ja) フッ素ゴム−金属積層ガスケット素材
JP2007284487A (ja) 加硫接着剤組成物
CN1527866A (zh) 涂料组合物及罐内面涂装方法
JP5407233B2 (ja) フッ素ゴム金属積層板
JP4483611B2 (ja) ニトリルゴム−金属積層ガスケット素材
US7311978B2 (en) Primer for vulcanization bonding
CN1694937A (zh) 硫化型粘合剂组合物
JP2006218630A5 (zh)
JP4876683B2 (ja) アクリルゴム−金属複合体
JP4393044B2 (ja) エンジン用シリンダヘッドガスケット素材
JP2007038533A (ja) ゴム金属積層体
JP2003261850A (ja) 加硫接着剤組成物
JP4131167B2 (ja) フッ素ゴム積層金属板
JP4626315B2 (ja) 加硫接着剤組成物
JP4407424B2 (ja) フッ素ゴム−金属積層ガスケット素材
JP4696568B2 (ja) プライマー組成物
JP2004277435A (ja) 加硫接着剤組成物
JP4175140B2 (ja) フッ素ゴム積層金属板
JP2008075808A (ja) 船舶用（水素化）ニトリルゴム−金属積層ガスケット素材
JP5428490B2 (ja) ニトリルゴム金属積層体

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CX01 Expiry of patent term

Granted publication date: 20070718

CX01 Expiry of patent term