阅读说明：本技术 一种增粘剂及其制备方法和硅橡胶组合物 (Tackifier, preparation method thereof and silicone rubber composition ) 是由 梁杰旭 叶文波 张虎 雷有金 刘强 于 2020-04-20 设计创作，主要内容包括：本发明的一种增粘剂及其制备方法和硅橡胶组合物,其技术方案要点是公开了具有式Ⅰ所示结构的分子结构式,其式1中,Me为甲基,R选自苯基、萘基或环己基；3≤n。该增粘剂能够有效的提高硅橡胶与基材的粘接效果,能够明显提高硅橡胶与基材的粘接性,并且具有良好的金属脱模性,实验结果表明,该增粘剂用量少,对硅橡胶的其他性能没有影响。(The invention discloses a tackifier, a preparation method thereof and a silicone rubber composition, and the technical scheme of the tackifier is characterized in that the tackifier has a molecular structural formula shown in a formula I, wherein in the formula 1, Me is methyl, and R is selected from phenyl, naphthyl or cyclohexyl; n is more than or equal to 3. The tackifier can effectively improve the bonding effect of the silicone rubber and the base material, can obviously improve the bonding property of the silicone rubber and the base material, and has good metal demolding property.)

1. The tackifier for the addition type liquid silicone rubber is characterized by having the following molecular formula structure:

wherein Me is methyl, and R is selected from phenyl, naphthyl or cyclohexyl;

3≤n≤10。

2. the adhesion promoter of claim 1, wherein n is 3 to 9.

3. A method for preparing the tackifier of any one of claims 1 to 2, comprising the steps of:

a) mixing a compound with a structure shown in a formula II with toluene and a platinum catalyst to obtain a first mixture; mixing a compound with a structure shown in a formula III with toluene to obtain a second mixture;

r is phenyl, naphthyl or cyclohexyl;

b) and (3) dropwise adding the second mixture into the first mixture at the temperature of 30-80 ℃ for reaction to obtain the tackifier with the structure shown in the formula I.

4. The method for preparing the adhesion promoter as claimed in claim 3, wherein the platinum catalyst in the step a) is one or more selected from Speier catalyst, Karstedt catalyst and Lamoreaux catalyst.

5. The preparation method of the adhesion promoter as claimed in claim 3, wherein the amount of the platinum catalyst used in the step a) is 5-30 ppm of the total mass of all raw materials, and the mass ratio of the compound to toluene is 1: 1.

6. The preparation method of the tackifier according to claim 3, wherein the reaction temperature in the step b) is 65-75 ℃.

7. A silicone rubber composition comprising a silicone rubber and an adhesion promoter;

the tackifier is prepared by the preparation method of any one of claims 1 to 2 or any one of claims 3 to 6, and the mass ratio of the silicone rubber to the tackifier is 100: 1.

[ technical field ] A method for producing a semiconductor device

The invention belongs to the technical field of addition type liquid silicone rubber and an auxiliary agent thereof, and particularly relates to a tackifier, a preparation method thereof and a silicone rubber composition.

[ background of the invention ]

Although the addition type liquid silicone rubber has the advantages of high and low temperature resistance, weather aging resistance, ozone resistance, electric insulation, flame resistance, no toxicity, no corrosiveness, physiological inertia and the like, the adhesion of the common silicone rubber to various base materials is generally poor, and the industrial requirement is difficult to meet.

Currently, in order to improve adhesion of silicone rubber to a substrate, the following three methods are generally used: firstly, coating priming paint on the surface of a resin substrate, and then further coating silicon rubber to cure the resin substrate so as to realize the bonding of the silicon rubber and the substrate; (2) the molecular structure of the silicon rubber is improved, so that the cohesiveness of the silicon rubber is improved; (3) an adhesion promoter is introduced into the silicone rubber to improve the adhesion between the silicone rubber and the substrate. The method using the primer and the modified silicon rubber molecular structure is complex in operation, long in time consumption and high in cost; the method for introducing the tackifier is simple and easy to implement, shortens the operation time, reduces the cost, improves the working efficiency, and becomes an effective method for improving the cohesiveness of the silicon rubber and the base material.

Although many tackifiers have been invented at present to effectively improve the adhesion of silicone rubber to conventional thermoplastic resins such as acrylonitrile-butadiene-styrene (ABS) resin, Polycarbonate (PC) resin, Polyethylene (PE) resin, polypropylene (PP) resin, etc., many patents report only the adhesion between silicone rubber and a substrate, and fail to solve the problems of mold sticking or mold release failure due to the addition of a tackifier. Therefore, these tackifier-added silicone rubbers have greatly reduced industrial application value.

[ summary of the invention ]

The invention aims to provide a tackifier for addition type liquid silicone rubber, which can effectively improve the bonding effect of silicone rubber and a base material and is easy to release.

The invention also provides a preparation method of the tackifier.

The invention also provides a silicone rubber composition containing the tackifier.

The tackifier disclosed by the invention has a structure shown in a formula I:

wherein Me is methyl, and R is selected from phenyl, naphthyl or cyclohexyl;

3≤n。

preferably, n is 3-9.

The invention provides a preparation method of a tackifier, which comprises the following steps:

a) mixing a compound with a structure shown in a formula II with toluene and a platinum catalyst to obtain a first mixture;

mixing a compound having a structure of formula III with toluene to obtain a second mixture;

3≤n≤9；

r is phenyl, naphthyl or cyclohexyl;

b) dripping the second mixture into the first mixture at the temperature of 30-80 ℃ for reaction to obtain the tackifier with the structure shown in the formula I,

preferably, the compound having the structure of formula ii is mixed with toluene and a platinum catalyst selected from one or more of Speier catalyst, Karstedt catalyst, and Lamoreaux catalyst to obtain a first mixture.

Preferably, the mass ratio of the compound having the structure of formula ii to toluene is preferably 1: 1; the platinum catalyst accounts for 5-30 ppm of the total mass of all the raw materials.

Preferably, the value of n in the compound with the structure of the formula II is 3-10, preferably 4-10, and more preferably 3, 6 or 9; preferably, the compound with the structure of the formula II is 1, 6-hexanediol dimethacrylate, 3- (2-methylprop-2-enoyloxy) propyl-2-methylprop-2-enoate or 2-methyl-2-propenoic acid-1, 9-nonanediol ester; the 1, 6-hexanediol dimethacrylate has a structure shown as a formula 201; the 3- (2-methylprop-2-enoyloxy) propyl-2-methylprop-2-enoate has a structure shown in a formula 202; the 1, 9-nonanediol 2-methyl-2-acrylate has the structure shown in formula 203:

preferably, the compound with the structure of the formula III and the toluene are mixed to obtain a second mixture, and the mass ratio of the compound with the structure of the formula III to the toluene is preferably 1: 1.

Preferably, the compound having the structure of formula iii is specifically phenyl tris (dimethylsiloxy) silane, naphthyl tris (dimethylsiloxy) silane or cyclohexyl tris (dimethylsiloxy) silane; the phenyl tri (dimethylsiloxy) silane has a structure represented by formula 301; the naphthalenyltris (dimethylsiloxy) silane has the structure shown in formula 302; the cyclohexyltris (dimethylsiloxy) silane has the structure shown in formula 303:

and c, after the first mixture and the second mixture are obtained in the step b, dropwise adding the second mixture into the first mixture at the temperature of 30-80 ℃ to react to obtain the tackifier with the structure shown in the formula I, wherein the reaction time of dropwise adding the second mixture into the first mixture is 2.5-3.5 h, and more preferably 3 h.

Preferably, the reaction temperature after the second mixture is added dropwise to the first mixture is 65 to 75 ℃.

Preferably, after cooling the reaction product in the step b, removing toluene by removing low-boiling-point substances to obtain the tackifier with the structure shown in the formula I, wherein the temperature for removing toluene is 100 ℃, and the pressure for removing toluene is preferably-0.95 MPa.

The silicone rubber composition comprises a silicone rubber and a tackifier; the tackifier is the tackifier prepared by the technical scheme, and the mass ratio of the silicone rubber to the tackifier is 100: 1.

Compared with the prior art, the invention has the beneficial effects that:

the invention provides a tackifier, which has a structure shown in a formula I, can obviously improve the adhesion between silicon rubber and a base material, and has good metal demolding property, and experimental results show that the tackifier is low in using amount and has no influence on other properties of the silicon rubber, the cohesive failure of the silicon rubber added with the tackifier to stainless steel and aluminum sheets can be ignored, and the cohesive failure to glass fiber PA, PEI, PPSU and PC is 80-100%;

the method provided by the invention has the advantages of mild conditions, simple process, strong operability, easy realization of industrial production and the like.

[ detailed description ] embodiments

The tackifier disclosed by the invention has a structure shown in a formula I:

wherein Me is methyl, and R is selected from phenyl, naphthyl or cyclohexyl;

3≤n。

in the invention, n is preferably 3-10; more preferably 3, 6, 9;

in a specific embodiment of the invention, the tackifier is specifically formula 101, formula 102, formula 103, formula 104, formula 105, formula 106, formula 107, formula 108, or formula 109:

the invention provides a preparation method of the tackifier according to the technical scheme, which comprises the following steps:

a) mixing a compound with a structure shown in a formula II with toluene and a platinum catalyst to obtain a first mixture;

mixing a compound having a structure of formula III with toluene to obtain a second mixture;

3≤n≤9；

r is phenyl, naphthyl or cyclohexyl;

b) and dropwise adding the second mixture into the first mixture at the temperature of 30-80 ℃ for reaction to obtain the tackifier.

In the present invention, the silicone rubber can be prepared as follows:

the preparation method of the component A comprises the following steps: 65 parts of dimethyl terminated by dimethylvinylsiloxy groupsPolysiloxane (viscosity at 25 ℃ C. is 30000mPa.s), 5 parts of trimethylsilanyl-terminated dimethylpolysiloxane having vinyl groups (vinyl value 0.096mmol/g), 25 parts of fumed silica (BET specific surface area 200 m)²(g, deyama, japan QS-20), 6 parts of methylsilazane, 2.5 parts of vinylsilazane, and 0.6 part of water were put into a kneader/mixer to be uniformly mixed and further heated and mixed at 150 ℃ for 3 hours to obtain a component a;

the preparation method of the component B comprises the following steps: uniformly mixing 1.8 parts of organohydrogenpolysiloxane (SiH content is 7mmol/g), 0.5 part of tetramethyldivinyl siloxane solution (concentration is 0.25 wt%) of chloroplatinic acid and 0.8 part of ethanol solution (concentration is 10 wt%) of ethynylcyclohexanol for 20min to obtain a component B;

the silicone rubber is obtained by uniformly mixing the A, B components prepared by the method.

The silicone rubber composition provided by the invention is tested for its adhesive strength and mold release properties according to the following methods:

100 parts of silicone rubber and 1 part of tackifier of formula I are mixed and stirred uniformly at room temperature to obtain the silicone rubber composition. The obtained silicone rubber composition was respectively molded with a glass fiber reinforced polyamide resin substrate (glass fiber PA), a polyetherimide resin (PEI) substrate, a polyphenylene sulfone resin (PPSU), and a polyethylene terephthalate (PC) substrate for 200s at a temperature of 120 ℃ and a pressure of 100MPa, and after cooling, the adhesive strength of the silicone rubber with various resin substrates and the releasability from a metal mold were tested.

The adhesive added to the silicone rubber and the preparation method are described in detail below with reference to examples: