WO2016109992A1 - 一种用于uv固化的有机硅组合物 - Google Patents

一种用于uv固化的有机硅组合物 Download PDF

Info

Publication number
WO2016109992A1
WO2016109992A1 PCT/CN2015/071408 CN2015071408W WO2016109992A1 WO 2016109992 A1 WO2016109992 A1 WO 2016109992A1 CN 2015071408 W CN2015071408 W CN 2015071408W WO 2016109992 A1 WO2016109992 A1 WO 2016109992A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
silicone
parts
curing
derivative
Prior art date
Application number
PCT/CN2015/071408
Other languages
English (en)
French (fr)
Inventor
陈维
张学超
王建斌
陈田安
Original Assignee
烟台德邦先进硅材料有限公司
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 烟台德邦先进硅材料有限公司 filed Critical 烟台德邦先进硅材料有限公司
Publication of WO2016109992A1 publication Critical patent/WO2016109992A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the invention relates to a silicone composition for UV curing, belonging to the fields of chemical industry and electronics.
  • the UV-curable silicone resin material is energy-saving and has a faster curing speed than conventional silicone materials. Compared with ordinary UV-curable organic resins, it has better temperature resistance, weather resistance and yellowing resistance. Therefore, the UV-curable silicone material can be used in a release coating (release agent), a fiber coating, an electronic packaging material, a film material, and the like.
  • photocurable silicone systems consist primarily of three components: a photosensitive polysiloxane (silicone prepolymer), a photoinitiator, and a reactive diluent.
  • a photosensitive polysiloxane silicone prepolymer
  • a photoinitiator silicon dioxide
  • a reactive diluent e.g., a reactive diluent
  • other fillers or auxiliaries may be added depending on the particular application.
  • the reactive diluent means a small molecule of an active monomer having an acryloyloxy group.
  • Conventional non-silicone monomers including monofunctional, difunctional, trifunctional and tetrafunctional monomers. As the number of reactive groups increases, the curing activity of the monomers increases, and the hardness of the cured materials increases.
  • Monofunctional monomers such as isobornyl acrylate (IBOA), hydroxyethyl acrylate, and isobutyl acrylate, generally have the disadvantages of high volatility and strong odor.
  • Bifunctional monomers such as tripropylene glycol diacrylate (TPGDA), 1,6-hexanediol diacrylate (HDDA), etc.
  • TPGDA tripropylene glycol diacrylate
  • HDDA 1,6-hexanediol diacrylate
  • the trifunctional monomer generally has a large viscosity and a high activity, but is highly irritating to the human body. Higher functionality monomers are also available in commercial products with a smaller range of applications.
  • the above monomers are inferior in compatibility with the UV-curable silicone resin system, and some of the monomers become cloudy after being mixed with the silicone component. Some monomers, although transparent after mixing with the silicone component, It turns white immediately after curing and cannot be used as an optically transparent material.
  • the above monomers have high volatility and are highly biotoxic. It is difficult to meet the requirements for electrical performance, heat resistance, and yellowing resistance in the field of electronic packaging.
  • Another disadvantage of the conventional non-silicone system UV-curing adhesive formulation is that due to the presence of a large number of double bonds in the system, the density change causes a large shrinkage during the UV-induced radical polymerization, and the shrinkage is 2 %about.
  • the silicone system for UV curing is more effective than the conventional UV-curable resin system. Therefore, the UV curing system of silicone is generally carried out in a nitrogen atmosphere, and the required curing energy is high.
  • the technical problem to be solved by the present invention is to provide a silicone composition for UV curing, which has excellent mechanical properties for the existing UV curing adhesive, such as large shrinkage, heavy odor, high toxicity, easy cracking and the like. It is safe and environmentally friendly, with high transparency, high strength and low shrinkage.
  • a silicone composition for UV curing characterized in that it consists of the following raw materials by weight:
  • the present invention can also be improved as follows.
  • the polysiloxane having a UV-reactive functional group at a double end has a molecular weight of 1,000 to 100,000, and the molecular formula is:
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each represent a hydrocarbyl group having 1 to 10 C atoms, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6
  • the hydrocarbyl groups represented are the same or different,
  • A represents a group having UV photocuring activity, and the group has an acryloyloxy group or a methacryloyloxy group, and the group represented by A includes one or more of the following structures:
  • R 7 represents an alkylene group having 1 to 10 C atoms, or R 7 represents an alkylene group having an oxygen atom spacing between carbon atoms, and examples of R 7 include: an alkylene group such as a methylene group or an ethylene group Base, propylene, 1-methylethylene, 1,4-butylene, 1-methyl-1,3-propylene, 2-methyl-1,3-propylene, 1,1 - one or more of dimethyl-ethylene and pentylene; arylene, such as phenylene; alkylene group, such as -CH 2 -CH 2 -CH 2 -OCH 2 -CH 2 -CH 2 -;
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each represent one or more of an alkyl group, an aryl group, an alkenyl group and an alkynyl group having 1 to 10 C atoms.
  • methyl, ethyl, propyl 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1 -methylbutyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, giga Base, octyl, decyl, decyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl, naphthyl, tolyl, xylyl, benzyl, phenethyl, vinyl, allyl, One or more of a propenyl group, a styryl group, a phenylpropenyl group, an ethynyl group, a propynyl group;
  • the R 7 represents an alkylene group having 1 to 6 C atoms, or an alkylene group having an oxygen atom spacing between carbon atoms.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each represent one or more of an alkyl group, an aryl group, an alkenyl group and an alkynyl group having 1 to 6 C atoms.
  • an alkyl group an aryl group, an alkenyl group and an alkynyl group having 1 to 6 C atoms.
  • a methyl group an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a cyclopentyl group, and a phenyl group.
  • the R 7 represents an alkylene group having 1 to 4 C atoms, or an alkylene group having an oxygen atom spacing between carbon atoms.
  • the silicone resin having a UV-reactive functional group has the following formula: [R 1 R 2 R 3 SiO 1/2 ] a [SiO 2 ] b [A-SiO 3/2 ] c ,
  • R 1 , R 2 , R 3 and A are as described above.
  • the UV-active silicone oligomer refers to a small molecule polysiloxane containing one or several acryloxypropyl or methacryloxypropyl groups directly bonded to a silicon atom for participation in UV Photoinitiated free radical polymerization with a viscosity of 1-500 mPa.s.
  • a silicone acrylate and silicone methyl group for UV curing resins See Chinese Patent 201310518918.0 "A silicone acrylate and silicone methyl group for UV curing resins".
  • the specification of the method for preparing acrylate monomer, the partial structure is as follows:
  • the radical photoinitiator is benzoin, benzoin derivative, benzilyl, benzoyl derivative, acetophenone, acetophenone derivative, benzophenone, benzophenone derivative One or more of a substance, a thioxanthone or a thioxanthone derivative.
  • the radical photoinitiator is benzophenone, 1-hydroxycyclohexyl phenyl ketone (trade name Irgacure 184, Ciba Specialty Chemicals Inc.), 2,2-dimethylhydroxyacetophenone (trade name) Darocure 1173, Ciba Specialty Chemicals Inc.), 2,2 dimethyl- ⁇ -hydroxy p-isopropylacetophenone (trade name: Darocure 1116, Merck & Co., Inc.), 1-hydroxycyclohexyl benzophenone, 2- Methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone (trade name) Irgacure 907, Beijing Yingli Technology Development Co., Ltd.), 2-hydroxy-2-methyl-1 phenyl-1-propanone, isopropyl thioxanthone, benzoin ether (trade name VIcure 10, BEHRINGER TECHNOLOGY CO., LTD.) One or several of them.
  • An advantage of the present invention is that the components of the formulation system have similar polarities, and no blushing occurs before or after curing, and a UV-curable silicone material having high transparency can be obtained, which is particularly suitable for use. Applications in the field of optics.
  • a second advantage of the present invention is that by adjusting the amount of the silicone resin having a UV-reactive functional group, a high-strength UV-curable silicone material having an adjustable performance within a certain range can be obtained.
  • a third advantage of the present invention is that by adjusting the amount of UV-active silicone oligomers, UV-curable silicone materials having different viscosities can be obtained.
  • a fourth advantage of the present invention is that a silicone light-resistant silicone material having low shrinkage, good temperature resistance, and yellowing resistance can be obtained by utilizing the characteristics of the silicone resin and the linear body.
  • Example 1a is an infrared spectrum of a terminal hydrogen polysiloxane prepared in Example 1 of the present invention
  • Figure 1b is an infrared spectrum of the polysiloxane DA-1 prepared in Example 1 of the present invention.
  • Example 2 is an infrared spectrum diagram of a silicone resin MA-2 prepared in Example 2 of the present invention
  • Example 3 is an infrared spectrum of a silicone oligomer TM-3 prepared in Example 3 of the present invention.
  • Figures 1a and 1b are infrared spectra of terminal hydrogen polysiloxane and DA-1, respectively.
  • Infrared spectrum (cm -1 ) of the terminal hydrogen polysiloxane 2963, 2127, 1413, 1258, 1014, 910, 864, 788, 701, 659.
  • Infrared spectrum (cm -1 ) of DA-1 2962, 1729, 1687, 1408, 1297, 1258, 1192, 1013, 864, 790, 702, 661.
  • a typical characteristic peak of a Si-H group is present at 2127 cm -1 .
  • Fig. 1b the peak of the Si-H group disappears, and a characteristic absorption peak of the acrylate group and the methylene group appears, which proves that the above-mentioned addition reaction occurs.
  • the vinyl MQ resin used in Table 1 was a commercial silicone MQ solid resin, which was purchased from Shanghai Jian Orange Co., Ltd. and had a vinyl content of 2% by weight.
  • the fumed silica model is R974. According to the representation in the field of rubber and plastic formulations, the amounts of the components in Table 1 are all parts by mass (phr).
  • the DA-1 was simply UV-cured, and the tensile strength was low, and there was almost no practical use. Reinforcing with a vinyl MQ resin is intended to improve its mechanical properties, but the vinyl group of the vinyl MQ resin cannot form an effective crosslink therewith, so that the surface of the resulting cured product is severely sticky.
  • fumed silica is added, the transparency of the system is lowered.
  • the silicone resin MA-2 is used to enhance the system, and it is possible to obtain a product with high tensile strength while achieving high optical transparency.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

本发明涉及一种用于UV固化的有机硅组合物，由如下重量份的原料组成：100份双端具有UV活性官能团的聚硅氧烷，10-30份具有UV活性官能团的有机硅树脂，5-10份具有UV活性的有机硅低聚体，0.1-10份自由基光引发剂。本发明提供一种用于UV固化的有机硅组合物，此有机硅组合物的机械性能优异、安全环保，具有高度透明性、高强度和低收缩率。

Description

一种用于UV固化的有机硅组合物 技术领域
本发明涉及一种用于UV固化的有机硅组合物，属于化工、电子领域。
背景技术
UV固化的有机硅树脂材料，与传统有机硅材料相比，其固化方式节能，且固化速度快。而与普通UV固化有机树脂相比，则有较好的耐温性、耐候性、耐黄变性。因此，UV固化有机硅材料可以用在离形涂料(隔离剂)、光纤涂料、电子封装材料、膜材料等方面。
一般来讲，光固化有机硅体系主要由3种组分组成：光敏性的聚硅氧烷(有机硅预聚物)、光引发剂和活性稀释剂。另外根据具体的用途，还可添加其它填料或助剂。
其中，活性稀释剂是指小分子的具有丙烯酰氧基的活性单体。传统的非有机硅类单体，包括单官能、双官能、三官能及四官能单体，随着活性基团数量的提高，单体的固化活性逐渐提高，固化得到的材料硬度也逐渐增大。单官能单体，如丙烯酸异冰片酯(IBOA)，丙烯酸羟乙酯，丙烯酸异丁酯，普通存在挥发性高，气味浓重的缺点。双官能基单体，如二缩三丙二醇二丙烯酸酯(TPGDA)、1,6-己二醇二丙烯酸酯(HDDA)等,刺激性较小，溶解力强，活性高，对基材的粘接力大。而三官能单体的粘度一般很大，活性高，但是对人体有较大的刺激性。更高官能度的单体也有商品化产品，其应用范围则更小。
上述单体与以UV固化的有机硅树脂体系相容性差，有的单体在与有机硅组分混合后即变浑浊。有的单体，在与有机硅组分混合后虽然透明，但是 固化后立即变白，无法作为光学透明材料使用。
另外，上述单体的挥发性高，生物毒性大。难以满足在应用于电子封装领域中对电气性能及耐热性、耐黄变性的要求。
传统的非有机硅体系的UV固化胶粘剂配方的另一个缺点是，由于体系中存在有大量的双键，在UV光引发的自由基聚合过程中，密度变化引起较大的收缩，收缩率为2％左右。
另外，由于有机硅本身的透氧性较高，用于UV固化的有机硅体系，相比普通的UV固化树脂体系受到氧气阻聚的效应更明显。因此，有机硅的UV固化体系一般是在氮气气氛中进行，且需要的固化能量较高。
发明内容
本发明所要解决的技术问题是，针对现有UV固化胶粘剂收缩率大、气味重、毒性高、易开裂等缺点，提供一种用于UV固化的有机硅组合物，本组合物的机械性能优异、安全环保，具有高度透明性、高强度和低收缩率。
本发明解决上述技术问题的技术方案如下：一种用于UV固化的有机硅组合物，其特征在于，由如下重量份的原料组成：
1)100份双端具有UV活性官能团的聚硅氧烷；
2)10-30份具有UV活性官能团的有机硅树脂；
3)5-10份具有UV活性的有机硅低聚体；
4)0.1-10份自由基光引发剂。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，所述双端具有UV活性官能团的聚硅氧烷的分子量为1000-100000，其分子通式为：
Figure PCTCN2015071408-appb-000001
其中，R1、R2、R3、R4、R5和R6分别代表具有1～10个C原子的烃基基团，R1、R2、R3、R4、R5和R6代表的烃基基团相同或不同，
A代表具有UV光固化活性的基团，该基团中具有丙烯酰氧基或甲基丙烯酰氧基，A代表的基团包括下列结构中的一种或几种：
Figure PCTCN2015071408-appb-000002
R7代表具有1～10个C原子的亚烃基团，或R7代表在碳原子之间有氧原子间隔的亚醚基，R7的实例包括：亚烷基，例如亚甲基、亚乙基、亚丙基、1-甲基亚乙基、1,4-亚丁基、1-甲基-1，3-亚丙基、2-甲基-1，3-亚丙基、1，1-二甲基-亚乙基、亚戊基中的一种或几种；亚芳基，如苯撑；亚醚基，如-CH2-CH2-CH2-OCH2-CH2-CH2-；
进一步，所述R1、R2、R3、R4、R5和R6分别代表具有1～10个C原子的烷基、芳基、链烯基、炔基中的一种或几种，例如：甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1，1-二甲基乙基、戊基、1-甲基丁基、1-乙基丙基、2-甲基丁基、3-甲基丁基、1，2-二甲基丙基、2，2-二甲基丙基、己基、庚基、辛基、壬基、癸基、环戊基、环己基、甲基环己基、苯基、萘基、甲苯基、二甲苯基、苄基、苯乙基、乙烯基、烯丙基、丙烯基、苯乙烯基、苯丙烯基、乙炔基、丙炔基中的一种或几种；
所述R7代表具有1～6个C原子的亚烃基，或在碳原子之间有氧原子间隔的亚醚基。
进一步，所述R1、R2、R3、R4、R5和R6分别代表具有1～6个C原子的烷基、芳基、链烯基、炔基中的一种或几种，例如：甲基、乙基、丙基、丁基、戊基、辛基、环戊基、苯基中的一种或几种。
所述R7代表具有1～4个C原子的亚烃基，或在碳原子之间有氧原子间隔的亚醚基。
进一步，所述具有UV活性官能团的有机硅树脂具有如下通式： [R1R2R3SiO1/2]a[SiO2]b[A-SiO3/2]c,
其中，R1、R2、R3和A代表的结构如上所述，
a、b和c分别代表有机硅树脂中结构单元所占的摩尔分数，a+b+c＝1,且0<c<1。
进一步，所述具有UV活性的有机硅低聚体指含有一个或几个与硅原子直接相连的丙烯酰氧丙基或甲基丙烯酰氧丙基的小分子聚硅氧烷，用于参与UV光引发的自由基聚合反应，粘度为1-500mPa.s,这些小分子聚硅氧烷的结构及制备方法参见中国专利201310518918.0《一种用于UV固化树脂的有机硅丙烯酸酯和有机硅甲基丙烯酸酯单体的制备方法》公开的说明书，部分结构如下所示：
Figure PCTCN2015071408-appb-000003
进一步，所述自由基光引发剂为苯偶姻、苯偶姻衍生物、苯偶酰基、苯偶酰基衍生物、苯乙酮、苯乙酮衍生物、二苯甲酮、二苯甲酮衍生物、硫杂蒽酮、硫杂蒽酮衍生物中的一种或几种。
进一步，所述自由基光引发剂为二苯甲酮、1-羟基环己基苯基酮(商品名Irgacure 184，Ciba Specialty Chemicals Inc.)、2,2-二甲基羟基苯乙酮(商品名Darocure 1173,Ciba Specialty Chemicals Inc.)、2，2二甲基-α-羟基对异丙基苯乙酮(商品名Darocure 1116，Merck&Co.,Inc.)、1-羟基环己基苯酮、2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮(商品名 Irgacure 907，北京英力科技发展有限公司)、2-羟基-2-甲基-1苯基-1-丙酮、异丙基硫杂蒽酮、安息香醚(商品名VIcure 10，百灵威科技有限公司)中的一种或几种。
本发明的有益效果是：
本发明的一个优点是配方体系中各组分的极性相近，无论在固化前还是固化后，都不会出现发白现象，能得到具有高透明性的UV光固化有机硅材料，特别适用于光学领域的应用。
本发明的第二个优点是通过调节具有UV活性官能团的有机硅树脂的量，能得到在一定范围内性能可调节的高强度UV光固化有机硅材料。
本发明的第三个优点是通过调节具有UV活性的有机硅低聚体的量，可以得到具有不同粘度的、操作性不同的UV光固化有机硅材料。
本发明的第四个优点是利用有机硅树脂及线性体的特性，能得到具有低收缩率的、耐温性好、耐黄变的UV光固化有机硅材料。
附图说明
图1a为本发明实施例1制备的端氢聚硅氧烷的红外谱图；
图1b为本发明实施例1制备的聚硅氧烷DA-1的红外谱图；
图2为本发明实施例2制备的有机硅树脂MA-2的红外谱图；
图3为本发明实施例3制备的有机硅低聚体TM-3的红外谱图；
具体实施方式
以下对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1双端具有UV活性官能团的聚硅氧烷DA-1的合成
向5-L三口瓶中加入粘度为10Pa.s的端氢聚硅氧烷(Si-H含量为0.003％)2000g，1,6-己二醇二丙烯酸酯20g,正庚烷500mL,含量为 5000ppm的铂-乙烯基聚硅氧烷配合物1g,配以机械搅拌和温度计、置于加热油浴中，加热至70℃搅拌反应5小时。停止加热及搅拌，将反应混合物减压蒸馏除去溶剂，得到无色透明的双端具有UV活性官能团的聚硅氧烷DA-1。
图1a和1b分别是端氢聚硅氧烷及DA-1的红外谱图。端氢聚硅氧烷的红外谱图(cm-1)：2963，2127，1413，1258，1014，910，864，788，701，659。DA-1的红外谱图(cm-1)：2962，1729，1687，1408，1297，1258，1192，1013，864，790，702，661。在图1a中，2127cm-1处有Si-H基团的典型特征峰。而在图1b中，Si-H基团的峰消失，且出现丙烯酸酯基以及亚甲基的特征吸收峰，证明发生了上述加成反应。
实施例2具有UV活性官能团的有机硅树脂MA-2的合成
向5-L三口瓶中加入248.35g甲基丙烯酰氧丙基三甲氧基硅烷、1065.54g四甲氧基硅烷、162.38g六甲基二硅氧烷、310g硫酸水溶液(2wt％)、1500mL正庚烷，配以机械搅拌、温度计、dean-stark管和冷凝管、接收瓶，将混合物在室温下搅拌2小时后，液体温度升高到40℃，此时将油浴加热温度升高到70℃，搅拌反应2小时后，继续升温蒸馏生成的甲醇，直到液体温度升至80℃，停止搅拌与加热，待反应混合物降至室温后，向反应产物中加入7.09g氢氧化钾、1500mL正庚烷以及30mL水，继续升温油浴温度至80℃，并保温搅拌8小时。停止加热及搅拌，静置过夜。将反应混合物以水洗至中性，减压蒸馏除去溶剂，得到总质量为750.43g(产率为98.4％)透明的无色不挥发性液体硅树脂，粘度为20Pa.s,折射率为1.4103，命名为MA-2.
MA-2的红外谱图(图2)(cm-1)：2960，2927，2856，1732，1408，1252，1186，1051，863，838，755，690，其理论结构式如下：
Figure PCTCN2015071408-appb-000004
实施例3具有UV活性的有机硅低聚体TM-3的合成
向一个配有恒压漏斗、磁力搅拌、氮气保护的500mL的三口瓶中，加入117.16g(0.5mol)丙烯酰氧丙基三甲氧基硅烷，0.15g三氟甲磺酸，0.15g BHT,加热至50℃，通过恒压漏斗向反应瓶中滴加198.35g(1.5mol)乙酰氧基三甲基硅烷。滴加完成后，搅拌反应2小时，升温到80℃，将生成的乙酸甲酯蒸出。反应完毕后，将反应产物转移到分液漏斗中，加150mL正庚烷，以每次100mL水洗6次，得到中性的溶液。减压旋转蒸发得到189.27g丙烯酰氧丙基三(三甲基硅氧基)硅烷,命名为TM-3，产率为92.6％。红外谱图(cm-1)：2945，2841，1725，1638，1487，1408，1296，1263，1187，1079，985，810，671，611。
Figure PCTCN2015071408-appb-000005
实施例4UV固化有机硅材料配方及固化实验
为了说明本发明的有益成果，通过配方进行对比实验，配方组成及固化后性能见表1。
表1中所使用的乙烯基MQ树脂是商品化的有机硅MQ固体树脂，采购自上海建橙公司，其乙烯基含量为2wt％。气相法二氧化硅型号为R974。根据橡塑配方领域的表示方法，表1中各组分的量均为质量份数(phr)。
按表1中的比例对各组分充分混合后，根据GB/T528-2009要求制作片材，将混合物在模具内流平。在高压汞灯下进行UV光固化；
根据GB/T528-2009要求制作哑铃状硅胶样件，用拉力机测试拉伸强度；
表1
Figure PCTCN2015071408-appb-000006
从表1可以看出，在使用1质量份的光引发剂1173情况下，单纯对DA-1进行UV光固化，其拉伸强度很低，几乎没有实际用途。使用乙烯基MQ树脂进行补强，目的是提高其机械性能，但是乙烯基MQ树脂的乙烯基无法与之形成有效交联，故得到的固化产物表面严重发粘。而加入气相法二氧化硅后，体系透明性下降。采用有机硅树脂MA-2对于体系进行增强，能在实现高度光学透明的同时，得到拉伸强度很高的产品。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (6)

  1. 一种用于UV固化的有机硅组合物，其特征在于，由如下重量份的原料组成：
    1)100份双端具有UV活性官能团的聚硅氧烷；
    2)10-30份具有UV活性官能团的有机硅树脂；
    3)5-10份具有UV活性的有机硅低聚体；
    4)0.1-10份自由基光引发剂。
  2. 根据权利要求1所述的有机硅组合物，其特征在于，所述双端具有UV活性官能团的聚硅氧烷的分子量为1000-100000，其分子通式为：
    Figure PCTCN2015071408-appb-100001
    其中，R1、R2、R3、R4、R5和R6分别代表具有1～10个C原子的烃基基团，R1、R2、R3、R4、R5和R6代表的烃基基团相同或不同，
    A代表具有UV光固化活性的基团，该基团中具有丙烯酰氧基或甲基丙烯酰氧基，A代表的基团包括下列结构中的一种或几种：
    Figure PCTCN2015071408-appb-100002
    R7代表具有1～10个C原子的亚烃基团，或R7代表在碳原子之间有氧原子间隔的亚醚基。
  3. 根据权利要求2所述的有机硅组合物，其特征在于，所述R1、R2、R3、R4、R5和R6分别代表具有1～10个C原子的烷基、芳基、链烯基、炔基中的一种或几种。
  4. 根据权利要求2-3任一所述的有机硅组合物，其特征在于，所述具有UV活性官能团的有机硅树脂具有如下通式：[R1R2R3SiO1/2]a[SiO2]b[A-SiO3/2]c,
    其中，R1、R2和R3代表的结构如权利要求2或权利要求3所述，
    A代表的基团如权利要求2所述，
    a、b和c分别代表有机硅树脂中结构单元所占的摩尔分数，a+b+c＝1,且0<c<1。
  5. 根据权利要求4所述的有机硅组合物，其特征在于，所述具有UV活性的有机硅低聚体指含有一个或几个与硅原子直接相连的丙烯酰氧丙基或甲基丙烯酰氧丙基的小分子聚硅氧烷，粘度为1-500mPa.s。
  6. 根据权利要求5所述的有机硅组合物，其特征在于，所述自由基光引发剂为苯偶姻、苯偶姻衍生物、苯偶酰基、苯偶酰基衍生物、苯乙酮、苯乙酮衍生物、二苯甲酮、二苯甲酮衍生物、硫杂蒽酮、硫杂蒽酮衍生物中的一种或几种。
PCT/CN2015/071408 2015-01-05 2015-01-23 一种用于uv固化的有机硅组合物 WO2016109992A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510003200.7 2015-01-05
CN201510003200.7A CN104610696B (zh) 2015-01-05 2015-01-05 一种用于uv固化的有机硅组合物

Publications (1)

Publication Number Publication Date
WO2016109992A1 true WO2016109992A1 (zh) 2016-07-14

Family

ID=53145359

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/071408 WO2016109992A1 (zh) 2015-01-05 2015-01-23 一种用于uv固化的有机硅组合物

Country Status (2)

Country Link
CN (1) CN104610696B (zh)
WO (1) WO2016109992A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113307636A (zh) * 2020-02-27 2021-08-27 通用电气公司 具有光反应性-光稳定性混合粘结剂的陶瓷浆料
CN113637329A (zh) * 2021-07-22 2021-11-12 广东工业大学 一种高生物相容性的光敏有机硅材料及其制备方法和在光固化3d打印中的应用
CN113637173A (zh) * 2021-09-26 2021-11-12 深圳先进技术研究院 一类改性含巯基液体硅树脂和无毒、无色、无味光固化液体硅橡胶及其制备方法和应用
CN113930217A (zh) * 2021-11-05 2022-01-14 成都拓利科技股份有限公司 一种高折射率可光固化有机硅胶粘剂及其制备方法和应用

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10604653B2 (en) * 2015-10-19 2020-03-31 Dow Toray Co., Ltd. Active energy ray curable hot melt silicone composition, cured product thereof, and method of producing film
CN105419634B (zh) * 2015-12-24 2017-12-15 佛山市华联有机硅有限公司 一种紫外光固化有机硅涂料的制备方法
JP6799070B2 (ja) * 2016-03-07 2020-12-09 ダウ シリコーンズ コーポレーション 光硬化性シリコーン組成物及びその硬化物
JP6481647B2 (ja) * 2016-03-22 2019-03-13 信越化学工業株式会社 紫外線硬化性シリコーン組成物、その硬化物、及び該組成物からなる光学素子封止材、並びに該光学素子封止材により封止された光学素子
CN107057366B (zh) * 2017-01-10 2020-10-23 广东信翼科技有限公司 一种可uv固化的有机聚硅氧烷组合物及其在制备半导体电子器件中的应用
JP6927298B2 (ja) * 2017-06-06 2021-08-25 信越化学工業株式会社 紫外線硬化型シリコーン粘着剤組成物およびその硬化物
CN107338021B (zh) * 2017-08-14 2020-04-24 深圳市新纶科技股份有限公司 一种返工胶水及其用于清除返工触摸屏loca残胶的用途
EP3885420B1 (en) * 2018-11-21 2023-11-29 Shin-Etsu Chemical Co., Ltd. Ultraviolet ray curable silicone adhesive composition and cured product thereof
EP3892701A4 (en) * 2018-12-04 2022-08-24 Shin-Etsu Chemical Co., Ltd. UV-CURING SILICONE ADHESIVE COMPOSITION AND CURED PRODUCT THEREOF
CN110713818B (zh) * 2019-11-11 2021-11-26 王安 一种紫外/湿气双重快速固化的聚硅氧烷粘合剂组合物
CN110982346A (zh) * 2019-12-12 2020-04-10 浙江福斯特新材料研究院有限公司 墨水组合物、封装结构及半导体器件
CN113025052B (zh) * 2019-12-25 2023-03-21 新特能源股份有限公司 Uv固化性有机硅组合物、制备方法及其应用
CN112940202B (zh) * 2021-02-02 2022-08-05 深圳深凯硅胶制品有限公司 酒瓶盖用硅胶及其制备方法以及酒瓶盖
CN113736087A (zh) * 2021-09-13 2021-12-03 北京天山新材料技术有限公司 有机硅树脂及其制备方法、有机硅导电胶组合物及有机硅导电胶

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63117024A (ja) * 1986-11-05 1988-05-21 Toshiba Silicone Co Ltd 紫外線硬化性シリコ−ン組成物
JPH07216232A (ja) * 1994-01-28 1995-08-15 Shin Etsu Chem Co Ltd 紫外線硬化型オルガノポリシロキサン組成物
JP2008094877A (ja) * 2006-10-06 2008-04-24 Shin Etsu Chem Co Ltd 紫外線硬化型熱伝導性シリコーン組成物
CN101747860A (zh) * 2009-12-15 2010-06-23 陈俊光 大功率led的紫外线固化单组分有机硅封装胶
CN103189451A (zh) * 2010-12-22 2013-07-03 迈图高新材料日本合同公司 紫外线固化型有机硅树脂组合物及使用其的图像显示装置
JP2014001342A (ja) * 2012-06-20 2014-01-09 Momentive Performance Materials Inc 紫外線硬化型シリコーン樹脂組成物、及びそれを用いた画像表示装置

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102807757A (zh) * 2012-07-31 2012-12-05 烟台德邦先进硅材料有限公司 一种igbt模块封装用的有机硅凝胶及其制备方法
CN103554169B (zh) * 2013-10-29 2016-03-16 烟台德邦先进硅材料有限公司 一种用于uv固化树脂的有机硅丙烯酸酯和有机硅甲基丙烯酸酯单体的制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63117024A (ja) * 1986-11-05 1988-05-21 Toshiba Silicone Co Ltd 紫外線硬化性シリコ−ン組成物
JPH07216232A (ja) * 1994-01-28 1995-08-15 Shin Etsu Chem Co Ltd 紫外線硬化型オルガノポリシロキサン組成物
JP2008094877A (ja) * 2006-10-06 2008-04-24 Shin Etsu Chem Co Ltd 紫外線硬化型熱伝導性シリコーン組成物
CN101747860A (zh) * 2009-12-15 2010-06-23 陈俊光 大功率led的紫外线固化单组分有机硅封装胶
CN103189451A (zh) * 2010-12-22 2013-07-03 迈图高新材料日本合同公司 紫外线固化型有机硅树脂组合物及使用其的图像显示装置
JP2014001342A (ja) * 2012-06-20 2014-01-09 Momentive Performance Materials Inc 紫外線硬化型シリコーン樹脂組成物、及びそれを用いた画像表示装置

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113307636A (zh) * 2020-02-27 2021-08-27 通用电气公司 具有光反应性-光稳定性混合粘结剂的陶瓷浆料
CN113637329A (zh) * 2021-07-22 2021-11-12 广东工业大学 一种高生物相容性的光敏有机硅材料及其制备方法和在光固化3d打印中的应用
CN113637329B (zh) * 2021-07-22 2022-06-14 广东工业大学 一种高生物相容性的光敏有机硅材料及其制备方法和在光固化3d打印中的应用
CN113637173A (zh) * 2021-09-26 2021-11-12 深圳先进技术研究院 一类改性含巯基液体硅树脂和无毒、无色、无味光固化液体硅橡胶及其制备方法和应用
CN113930217A (zh) * 2021-11-05 2022-01-14 成都拓利科技股份有限公司 一种高折射率可光固化有机硅胶粘剂及其制备方法和应用

Also Published As

Publication number Publication date
CN104610696B (zh) 2017-05-24
CN104610696A (zh) 2015-05-13

Similar Documents

Publication Publication Date Title
WO2016109992A1 (zh) 一种用于uv固化的有机硅组合物
EP2800790B1 (en) Free radical polymerizable compositions comprising ionic silicones
CN104559196B (zh) 一种无色透明的光固化3d打印材料
Bayramoğlu et al. Synthesis and characterization of UV-curable dual hybrid oligomers based on epoxy acrylate containing pendant alkoxysilane groups
JP6927298B2 (ja) 紫外線硬化型シリコーン粘着剤組成物およびその硬化物
TWI397558B (zh) A method for producing a composite molded product of a hardened silicone rubber composition and a liquid crystal polymer and a silicone rubber
CN110183665B (zh) 一种含巯基mtq树脂的制备方法及其应用
CN108384014A (zh) 一种加成型硅橡胶用有机硅含氢增粘交联剂及其制备方法
CN107955581B (zh) 一种环氧有机硅改性光固化led封装胶及其制备方法
CN103819677B (zh) 笼型倍半硅氧烷化合物、使用它的固化性树脂组合物和树脂固化物
JPH06166740A (ja) ペンダントシリコーン樹脂を担持するｕｖ硬化性エポキシシリコーン
CN110713818B (zh) 一种紫外/湿气双重快速固化的聚硅氧烷粘合剂组合物
CN105001422B (zh) 一种加成型硅橡胶用增粘剂及其制备方法和加成型硅橡胶
US10940105B2 (en) Resin-linear organopolysiloxane block copolymer, use of same, and method for producing same
TW200427782A (en) Silicone resin composition and moldings thereof
Zheng et al. Fabrication of UV-curable fluorosilicone coatings with impressive hydrophobicity and solvent resistance
CN103360540A (zh) 一种长侧链的有机硅改性含氟（甲基）丙烯酸树脂
CN103554169A (zh) 一种用于uv固化树脂的有机硅丙烯酸酯和有机硅甲基丙烯酸酯单体的制备方法
KR20160024783A (ko) 수성 실란 커플링제 조성물, 그의 제조 방법 및 표면 처리제
CN113105605A (zh) 一种uv固化高透明poss改性有机硅-蓖麻油聚氨酯材料及其制备和应用
TW201546187A (zh) 加成硬化型聚矽氧組成物及光學元件
CN110023445A (zh) 液体粘合剂组合物、粘合剂片材和粘合剂粘合方法
TW202035490A (zh) 有機聚矽氧烷、紫外線固化性矽酮組合物及其固化物
CN108794750B (zh) 一种具有（甲基）丙烯酸酯基的聚硅氧烷及其制备方法和应用
TW201809146A (zh) 含有金屬非質子性有機矽烷氧化物化合物之配方

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15876500

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15876500

Country of ref document: EP

Kind code of ref document: A1