JP2011524432A - Pressure sensitive adhesive silicone composition - Google Patents

Abstract

The present invention relates to an MQ (OH) -type hydroxylated silicone resin A, a hydroxylated silicone rubber B, and a vinyl functional silicone resin E of MQ type or MQ (OH) type having D ^Vi and / or M ^Vi units. And a third component. The present invention also provides a method for producing the silicone composition, a composite comprising a support at least partially covered with the crosslinked silicone composition, and adhesion of the silicone composition on the support. It is also related to the use for completely or partially covering the surface of the support for the purpose.

Description

  The present invention relates to a pressure-sensitive adhesive composition containing silicone as a main component, a production method thereof, and use thereof.

  Generally, a pressure sensitive adhesive composition is represented by the acronym PSA for “pressure-sensitive adhesive”. Thus, in the present case, these are “silicone PSA” compositions.

  A pressure sensitive adhesive is an adhesive that can be adhered to a surface simply by contact or under the action of slight pressure. There are several types of pressure sensitive adhesives, including certain silicone compositions. Silicone PSA has certain advantages compared to other types of PSA. Silicone PSAs can be used over a wide range of temperatures, and these are compositions (resistant to moisture, solvents, acids, UV radiation) that are resistant to harsh physical or chemical conditions. They withstand microbial attack. Silicone PSA has excellent dielectric properties. Furthermore, they also adhere to surfaces that are difficult to follow, including polyester, polyimide, printed circuits, and the like.

  Brewster Silicones, Inc. offers an advanced silicone PSA composition under the trade name Rhodorsil® 400 which contains a toluene solution of a hydroxyl functional silicone resin of the MQ (OH) type and an α, ω-hydroxyl linear silicone rubber. Is selling. Here, the term “sophistication” is generally assumed to mean partial condensation of SiOH groups obtained by heating.

  U.S. Pat. No. 5,602,214 describes a silicone pressure sensitive adhesive composition comprising not only MQ (OH) type hydroxyl functional silicone resin and α, ω-hydroxyl linear silicone rubber, but also silicone oil.

French Patent No. 2705355 includes
A hydroxyl functional MQ siloxane resin which may or may not be an alkenyl functional group;
Hydroxyl functional silicone rubber,
A composition is described which can be used as a composition for pressure sensitive adhesives obtained by mixing with a hydroxyl functional silicone fluid of the MDT (OH) or DT (OH) type.

  This composition is not satisfactory from the viewpoint of the shear strength of a composite obtained by crosslinking such a composition.

  Furthermore, the difficulty of processing silicone resins has become an obstacle to using silicone PSA compositions. Indeed, the predetermined steps for producing these silicone PSA compositions are carried out at high temperatures and over several hours, which is a significant energy cost.

US Pat. No. 5,602,214 French Patent No. 2705355

  Accordingly, it would be desirable to have a silicone pressure sensitive adhesive composition whose performance as an adhesive is comparable or even improved to that of known silicone PSA compositions, particularly with respect to tack. The production cost of the adhesive composition should be advantageously reduced and the mechanical properties of the resulting cross-linked compound should also be improved.

  Coincidentally, after extensive research, the Applicant has developed a satisfactory silicone adhesive composition.

Therefore, the gist of the present invention is as follows:
MQ (OH) type hydroxyl functional silicone resin A (where M: R ¹ R ² R ³ SiO _1/2 and Q (OH) :( OH) SiO _3/2 , R ¹ , R ² And R ³ are each independently
A linear or branched alkyl group having 1 to 8 carbon atoms, which may be substituted with one or more halogen atoms; and an aryl or alkylaryl group having 6 to 14 carbon atoms )When,
Hydroxyl functional silicone rubber B;
A third component which is an MQ-type or MQ (OH) -type vinyl-functional silicone resin E, which contains D ^Vi and / or M ^Vi units (where M: R ¹ R ² R ³ SiO _{1 / 2} , M ^Vi : R ¹ R ² R ⁴ SiO _1/2 , D ^Vi : R ¹ R ⁴ SiO _2/2 , Q: SiO _4/2 and Q (OH) :( OH) SiO _3/2 The R ¹ , R ² and R ³ groups are each independently
A linear or branched alkyl group having 1 to 8 carbon atoms, optionally substituted with one or more halogen atoms; and an aryl or alkylaryl group having 6 to 14 carbon atoms; R ⁴ is a vinyl group. ).

Advantageously, the silicone composition is a hydroxyl-functional silicone resin C of the MDT (OH) or DT (OH) type, where M: R ¹ R ² R ³ SiO _1/2 , D: R ¹ R ² SiO _2/2 and T (OH) :( OH) R ¹ SiO _2/2 wherein the R ¹ , R ² and R ³ groups are each independently
A linear or branched alkyl group having 1 to 8 carbon atoms, which may be substituted with one or more halogen atoms; and an aryl or alkylaryl group having 6 to 14 carbon atoms . ) Is also included.

  This silicone composition may contain one or more organic solvents S.

The preferred silicone composition is:
-Condensation catalyst F; and-neutralizing agent G,
Preferably both are included.

  In this specification and in the claims, the definite or indefinite article, for example “a” in the expression “condensation catalyst”, is used in the plural (unless the context clearly indicates the opposite (numerical “1”)). It should be noted that “some” or “one or more” should also be understood. Unless otherwise indicated, it is desirable to give technical and scientific terms used their meanings generally accepted by those skilled in the art.

In the following, polyorganosiloxane (POS) oils, rubbers and resins are described conventionally using conventional notation for the various siloxy units using the symbols M, D, T and Q. In this notation, the silicon atom of the siloxy unit is involved in one (M), two (D), three (T) or four (Q) covalent bonds with many oxygen atoms. Yes. If the oxygen atom is shared between two silicon atoms, this is considered 1/2 and is not shown in the abbreviated formula. On the other hand, when the oxygen atom belongs to an alkoxy or hydroxyl group bonded to a silicon atom, this chemical functional group is shown between parentheses in the omitted formula. By default, the remaining bonds of silicon atoms are associated with carbon atoms. In general, hydrocarbon groups bonded to silicon by C—Si bonds are not mentioned, but this usually corresponds to an alkyl group, for example a methyl group. For example, the abbreviated formula T (OR) ₂ is a unit containing two alkoxy groups in which a silicon atom is bonded to three oxygen atoms, ie, an alkyldialkoxysiloxy unit RSi (OR) ₂ O _1/2. (Where R is an alkyl group). That is why when this hydrocarbon group is a specific functional group, it is represented by a superscript. For example, the abbreviation M ^Vi is a unit in which a silicon atom is bonded to an oxygen atom and one of the hydrocarbon-based groups forming a C—Si bond is a vinyl group, that is, a dialkylvinylsiloxy unit R ₂ Si (Vi). O _1/2 (wherein R represents an alkyl group).

  In these formulas, R can represent various saturated or unsaturated, especially aromatic hydrocarbon-based groups, which can be substituted with heteroatoms. The meaning of R will be specified in the description below.

  The expression “substantially linear” is a polyorganosiloxane oil consisting of D siloxy units which also contain T siloxy units and / or Q siloxy units, wherein T and Q siloxy units are one per 100 silicon atoms. It should be understood to mean less than or equal to.

  The expression “silicone resin” refers to a polysiloxane containing a significant proportion of T and / or Q siloxy units and optionally D and / or M siloxy units. The expression “significant percentage” is intended to mean units (mol%) of at least 5%, preferably more than 25%, in particular more than 30%.

  The expression “silicone rubber” is a polydialkylsiloxane having a high molecular weight, for example greater than 100,000 g / mol, preferably greater than 125,000, in particular greater than 200,000, in particular greater than 250,000 g / mol, whose ends are functionalized with reactive groups. The thing which may be made into.

In the present application and hereinafter, MQ (OH) type hydroxyl functional silicone resin A is M: R ¹ R ² R ³ SiO _1/2 , Q: SiO _4/2 and Q (OH) :( OH) SiO _A copolymer composed of _3/2 siloxy units. R ¹ , R ² and R ³ groups are each independently
Linear or branched alkyl groups having 1 to 8 carbon atoms, in particular 1 to 6 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl and n-hexyl groups, wherein one or more Halogen atoms, especially those optionally substituted by 2 or 3 halogen atoms (especially 3,3,3-trifluoropropyl groups); and aryl or alkyl having 6 to 14 carbon atoms Selected from aryl groups, especially phenyl, xylyl and tolyl groups.

  “Alkyl” groups are preferably lower for hydroxyl-functional silicone resins A having a carbon number in the range of 1-6, preferably 1-3 or 4, in the main chain. It is an alkyl group. This chain may be linear or branched and includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl and the like. These compounds may be substituted with aliphatic or cyclic hydrocarbon group or halogen.

  Hydroxyl functional silicone resin A is, for example, 40-80 mol% M units, 30-55 mol% Q units, 5-15 mol% Q (OH) units, and 0. Contains 5-4 wt% -OH hydroxyl units.

Its Brookfield viscosity is in particular from 10 to 40 mm ² / s.

Under preferential conditions for practicing the present invention, the hydroxyl functional silicone resin A is 45-55 mol% M units, 38-45 mol% Q units, 7-10 mol% Q (OH). It contains 2.3 to 3% by weight of —OH hydroxyl units relative to the dry weight of the unit and the resin, and its Brookfield viscosity is 12 to 18 mm ² / s.

  The hydroxyl-functional silicone rubber B is, for example, a high molar mass α, ω-dihydroxyl polydialkylsiloxane, preferably an α, ω-dihydroxyl polydimethylsiloxane having an average molecular weight Mn> 100000 g / mol, in particular Mn> 150,000 g / mol. It is.

  In polydialkylsiloxanes, the “alkyl” group is preferably a lower alkyl group having in the main chain from 1 to 10 carbon atoms, preferably from 1 to 3 carbon atoms. This chain may be linear or branched and includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl and the like. These compounds may be substituted with aliphatic or cyclic hydrocarbon group or halogen.

  The hydroxyl functional silicone rubber B can also be a statistical copolymer of polydimethylsiloxane and polymethylphenylsiloxane mainly having silanol groups located at the chain ends.

MQ or MQ (OH) type vinyl-functional silicone resins E containing D ^Vi and / or M ^Vi units, for example, preferably contain less than 5% by weight of Vi groups, preferably less than 0.4% by weight of OH. MD ^Vi Q (OH) and MM ^Vi Q (OH) resin (with respect to the dry matter of the resin). This resin can be predispersed in aromatic or aliphatic solvents, often 40-65% dry matter. The molar mass of this resin can be in the range of 2000 to 4000 g / mol, for example.

  This (these) can represent 1 to 20% by weight, advantageously 2 to 15% by weight, preferably 2.5 to 10% by weight, of the total dry weight of the crosslinkable silicone composition of the invention.

  When the silicone composition of the present invention comprises a hydroxyl functional silicone resin C, this is of the MDT (OH) or DT (OH) type, where the M, D and T units are preferably Methyl functional units or phenyl functional units, in particular methyl functional units.

  Hydroxyl functional silicone resin C is, for example, 15 to 30 mol% D units, 50 to 75 mol% T units, 0 to 20 mol% M units and 0.1 to 3 relative to the dry weight of the resin. Contains% by weight of —OH hydroxyl units.

Its Brookfield viscosity is in particular from 500 to 8000 mm ² / s, preferably from 800 to 1200 mm ² / s.

The silicone composition of the present invention per 100% silicone active material on a dry / dry basis, for example:
20 to 80% by weight, preferably 35 to 60% by weight, in particular 45 to 50% by weight of hydroxyl-functional silicone resin A;
20 to 80% by weight, preferably 30 to 55% by weight, in particular 35 to 45% by weight of hydroxyl-functional silicone rubber B;
1 to 20% by weight, advantageously 2 to 15% by weight, preferably 2.5 to 10% by weight of vinyl-functional silicone resin E; and 1 to 35% by weight, preferably 2 to 30% by weight, in particular 5 to 20% by weight, in particular 5 to 16% by weight of hydroxyl-functional silicone resin C
Can be included.

  When the silicone composition of the present invention contains one or more organic solvents S, these are, for example, aromatic or aliphatic solvents (hexane, heptane, etc.), preferably toluene, xylene or optionally alkylbenzene, or oil fractions. For example, it can be a dearomatized aliphatic hydrocarbon sold under the trade name Exxsol® D40 or D60 by Exxon. These solvents generally have a boiling point of 60-200 ° C.

  This (these) may comprise 20-80% by weight, advantageously 30-60% by weight, preferably 35-50% by weight, in particular 40-60% by weight of the total weight of the crosslinkable silicone composition according to the invention. it can.

  Condensation catalysts F that can be used are, for example, alkali metals, amines or organometallic salts, preferably alkaline bases such as KOH and NaOH, optionally in aqueous solution, in particular one of these bases (eg KOH) and one ( Or one or more) silanolates obtained by reaction with silicone oligomers.

  Does the catalyst use its effectiveness in consideration of silanols, the temperature of the conversion reaction, and techniques that can facilitate the removal of water formed by the condensation of these silanols (redistillers, Dean Stark equipment, etc.)? Depends on how. These (these) can occupy from 10 to 2000 ppm, preferably from 20 to 1500 ppm, in particular from 35 to 1500 ppm of the total weight of the dry silicone composition according to the invention, based on the weight, relative to the dry silicone mixture.

  Neutralizing agents G that can be used are, for example, reaction products of organic acids or mineral acids, preferably phosphoric acid or acetic acid or carbonic acid, in particular phosphoric acid with one (or more) silicone oligomer.

  The amount of neutralizing agent added will, of course, depend on the amount of condensation catalyst used for the conversion reaction. It is necessary to adjust this addition amount with a view to obtaining a slight excess of acid relative to the amount of base introduced for good neutralization of the silicone PSA, or optionally conversion. . The conversion quality of silicone PSA can be monitored by examining residual silanols.

  Typically, PSA is sold in a relatively concentrated state (typically containing less than 50% by weight of solvent), and coating users generally determine the thickness of the silicone deposit on the support. To adjust, depending on the user's coater, dilution with a solvent such as PSA and toluene is performed shortly before the coating operation is performed.

  Accordingly, the present invention relates to the above composition diluted by adding, for example, a predetermined volume of a solvent, and the diluted composition is 20 to 60% by weight, preferably 25 to 55% by weight as a silicone solid content. In particular, it is intended to contain 30 to 50% by weight.

  During the bath formulation, radical pathways such as peroxide, which often allow the applicator to initiate cross-linking agents, particularly complementary cross-linking on the support as it enters the oven. A reagent which crosslinks with is added. Accordingly, preferred silicone compositions of the present invention also contain one or more cross-linking agents, particularly those that cross-link by radical pathways such as peroxides, for example 2,4-dichlorobenzoyl peroxide (DCB) peroxide.

The silicone composition is generally in an organic solvent S,
MQ (OH) type hydroxyl functional silicone resin A (where M: R ¹ R ² R ³ SiO _1/2 and Q (OH) :( OH) SiO _3/2 , R ¹ , R ² And R ³ are each independently
A linear or branched alkyl group having 1 to 8 carbon atoms, which may be substituted with one or more halogen atoms; and an aryl or alkylaryl group having 6 to 14 carbon atoms )When,
Hydroxyl functional silicone rubber B;
MQ type or MQ (OH) type vinyl functional silicone resin E containing D ^Vi and / or M ^Vi units (where M: R ¹ R ² R ³ SiO _1/2 , M ^{Vi : R 1 R 2 R 4 SiO} 1/2, D Vi: R 1 R 4 SiO 2/2, Q: SiO 4/2 and Q (OH) :( OH) a SiO _3/2, wherein R ^1, R ² and R ³ groups are each independently
A linear or branched alkyl group having 1 to 8 carbon atoms, which may be substituted with one or more halogen atoms; and an aryl or alkylaryl group having 6 to 14 carbon atoms;
Selected from
R ⁴ is a vinyl group. )
And can be manufactured by mixing them.

In addition, MDT (OH) or DT (OH) type hydroxyl functional silicone resin C (where M: R ¹ R ² R ³ SiO _1/2 , D: R ¹ R ² SiO _2/2 And T (OH) :( OH) R ¹ SiO _2/2 , wherein the R ¹ , R ² and R ³ groups are each independently
A linear or branched alkyl group having 1 to 8 carbon atoms, which may be substituted with one or more halogen atoms; and an aryl or alkylaryl group having 6 to 14 carbon atoms . )
It is also possible to incorporate.

  It is also possible to add optional components, that is, the condensation catalyst F and subsequently the neutralizing agent G.

  Moreover, it is also possible to mix | blend the optional condensing agent with the said mixture.

  Finally, it is also possible to mix a solvent with the above mixture.

The silicone composition can be produced in particular as follows:
(A) In organic solvent S, MQ (OH) type hydroxyl functional silicone resin A, hydroxyl functional silicone rubber B, and MQ or MQ (OH) type vinyl containing D ^Vi and / or M ^Vi units Mix the functional silicone resin E with the hydroxyl functional silicone resin C of the MDT (OH) or DT (OH) type, and then optionally mix the entire mixture at high temperature; Still, the condensation catalyst F is added at a high temperature, and the mixture is allowed to stand until the condensation reaction occurs, and then the neutralizing agent G is added to the mixture to obtain the desired composition.
(B) in organic solvent S, MQ (OH) type hydroxyl functional silicone resin A, hydroxyl functional silicone rubber B, and MQ or MQ (OH) type vinyl containing D ^Vi and / or M ^Vi units. The functional silicone resin E is mixed and the whole assembly is mixed at a high temperature, followed by the addition of the condensation catalyst F at a high temperature and leaving it until the condensation reaction occurs, and then the neutralizing agent G is added to the mixture. Subsequently, optionally MDT (OH) or DT (OH) type hydroxyl-functional silicone resin C is added to obtain the desired composition, which is cross-linked by a cross-linking agent, especially by a radical route, if necessary. Reagents or organic solvents or both are added to obtain a coating bath that allows the desired thickness of the silicone deposit to be obtained after evaporation of the solvent. The solids content of this bath is typically approximately 25-50% silicone so as to obtain a final (dry) silicone deposit of tens of micrometers (eg, 30-60 μm). These values are merely examples, and depend on the target application characteristics.
(C) In an organic solvent S, a hydroxyl functional silicone resin A of MQ (OH) type and a hydroxyl functional silicone rubber B are mixed, and these are mixed into MDT (OH) or DT (OH) type. Add hydroxyl functional silicone resin C and ^Dv and / or MQ or MQ (OH) type vinyl functional silicone resin E containing ^Vi units and leave until condensation reaction occurs, then as needed A coating agent is obtained in the same manner as (b) by adding a crosslinking agent, particularly an agent or an organic solvent that crosslinks by a radical route, or both.

MQ (OH) type hydroxyl functional silicone resin A, hydroxyl functional silicone rubber B, and MQ or MQ (OH) type vinyl functional silicone resin E containing D ^Vi and / or M ^Vi units When mixing at a high temperature in S, it is possible to carry out the mixing at a temperature close to the boiling point of the organic solvent, that is, a temperature equal to the boiling point of the solvent ± 5 ° C.

  Recover and separate the aqueous phase from the solvent to facilitate the condensation of the silanol, which can facilitate removal of the water formed, for example, commonly referred to as a “Dean Stark” or “re-distillation” device It is possible to use an apparatus in which the solvent is recycled to the reactor.

  The silicone composition that is the subject of the present invention has very advantageous properties and qualities. These can be crosslinked into pressure sensitive adhesives that make it reasonable to use them for the production of silicone pressure sensitive adhesive compositions.

  On the other hand, the silicone pressure-sensitive adhesive composition of the present invention is particularly endowed with remarkable adhesive properties, peel strength properties and shear strength properties.

  In fact, the main properties of PSA compositions are stickiness, peel strength and shear strength. Tackiness characterizes the adhesive strength of a pressure sensitive adhesive and requires the following two factors. That is, the nature of the bond with the support created instantaneously and the viscoelasticity of the adhesive. Peel strength makes it possible to evaluate the force required to separate the adhesive tape from its support. Shear strength makes it possible to measure the resistance of an adhesive subjected to shear forces imposed by a hanging weight at ambient temperature. There are a variety of reference measurements known to those skilled in the art.

  These characteristics are illustrated in the experimental part below. These not only provide the value of using the crosslinkable silicone composition to provide adhesion to the entire or partial coating on the surface of the support, but are also pre-loaded with peroxides. Crosslinking is carried out by completely or partially coating the surface with the crosslinkable silicone composition, followed by heating the silicone treated support at a temperature that allows removal of the solvent and activation of the peroxide used. Even in the method for imparting adhesive force on the support, the above-mentioned crosslinkable silicone composition is worth using.

  As such, another aspect of the present invention is a composite comprising a support that is at least partially covered with the crosslinked silicone composition.

  This support can be of very different nature depending on the field of application. For example, a support having a high surface energy such as metal, aluminum, or glass can be used. Moreover, for example, plastics such as a film made of polyester, polyimide, polyethylene terephthalate, or a predetermined polydimethylsiloxane are also included.

  Depending on the type of support, various technologies could be introduced.

  In particular, for flat supports such as sheets, films, strips etc., it would be possible to use an applicator, in particular an applicator with a roller.

  The preferred processing conditions of the crosslinkable silicone composition also apply to the other aspects of the invention targeted above, in particular to composites comprising a support at least partially covered with the crosslinkable silicone composition. .

  The following examples illustrate the invention.

Materials and substances:
The following materials and substances were used:
A 1 liter glass reactor equipped with a Dean-Stark apparatus and a condenser;
・ Stainless steel scraping anchor type stirrer;
A heating bath comprising a hot fluid (silicone oil) and consisting of a stainless steel beaker placed on a magnetic stirrer hotplate;
· Me ₃ SiO _1/2 units (approximately 50 mol%), is composed of SiO ₂ units (about 40%) and Q (OH) units (about 10%), containing 60% of active material in toluene, Mn = MQ (OH) silicone resin (A) having 2800 g / mol, containing 2.5% by weight OH (based on dry resin) and having a viscosity of 15 mm ² / s;
An α, ω-dihydroxypolydimethylsiloxane rubber (B) having a consistency of 800 mm / 10 and having Mn = 330000 g / mol;
60% xylene composed of MD ^Vi Q (OH) units, containing 2.5% Vi and 0.3% OH based on the weight of the dry resin and having a molar mass Mn = 3270 g / mol Silicone resin (E) in solution;
- consists MDT (OH) units, MeSiO _3/2 units to about 64% expressed in terms of mole, it comprises 23% Me ₂ SiO units and 13% Me ₃ SiO _1/2 units, Mn = 1680 g / mol A silicone resin (C) having an R / Si ratio = 1.4 and having a OH of 0.5% (by weight) and a viscosity of 1000 mm ² / s;
-Toluene solution of condensation catalyst (F) (prepared immediately before the test): 2.7 g of the reaction product of KOH and siloxane oligomer (D4, M2) was diluted in 40 g of toluene. The initial reaction product was titrated with 14.5% KOH and had a density = 1.023;
-Neutralization solution (G) diluted with toluene (prepared immediately before the test): 6 g of the reaction product of H ₃ PO ₄ and siloxane oligomers (D4 and 47V3) was diluted with 61.9 g of toluene. The initial reaction product was titrated with 8.5% H ₃ PO ₄ and had a density = 1.580.

Contrast:
The viscosity of these PSA is measured at the speed of needles 5 and 2.5 using a Brookfield DV-II + instrument.
The solids content of the PSA is determined from approximately 1 g of PSA by measuring the weight loss after standing in a ventilated oven at 150 ° C. for 1 hour.

Manufacturing:
Example 1 Preparation of a Pressure Sensitive Adhesive (PSA) Composition According to the Invention 500 g MQ (OH) resin (A) and 255 g toluene are introduced into the reactor and then stirring is started at a rate of 110 rpm.
Silicone rubber (B) (255 g) is added in portions and stirred for 1 hour.
When the heating bath is in operation and the temperature of the reaction mixture reaches 113 ° C., 6.78 g of the condensation catalyst dilution is introduced. After stirring for 4 hours under toluene reflux, the catalyst is neutralized by introducing 9.05 g of neutralizing solution. After 20 minutes, the heating bath is removed and the mixture is left to cool. A crosslinkable base composition (referred to as CBR1) is obtained.
An aliquot of the resulting 40.00 g base composition CBR1 was removed, followed by 1.00 g MD ^Vi Q (OH) resin (E), 0.63 g peroxide 2, with further stirring and low temperature. 4-Dichlorobenzoyl (DCB) and 20.54 g of toluene are added.
The resulting pressure sensitive adhesive composition is filled into a glass vial.

Examples 2-6: Preparation of Pressure Sensitive Adhesive (PSA) Composition According to the Invention The procedure of Example 1 was followed except that the base composition CBR1, toluene, DCB and MD ^Vi Q (OH ) The amount of resin (E) (expressed in g) was used.

Comparative Example 1: Preparation of Pressure Sensitive Adhesive (PSA) Composition Containing No MD ^Vi Q (OH) Resin (E) An aliquot of 40.00 g of the base composition CBR1 obtained in Preparation Example 1 was removed and 63 g of peroxidized DCB and 20.54 g of toluene are added with stirring and at low temperature.
The resulting control pressure sensitive adhesive composition is filled into glass vials.

Example 7: Preparation of a pressure sensitive adhesive (PSA) composition according to the invention 709.85 g MQ (OH) resin (A) and 403.75 g toluene are introduced into the reactor and then stirring is started at a rate of 110 rpm. To do.
Silicone rubber (B) (386.40 g) is added in portions and stirred for 1 hour. The temperature reached by self-heating is approximately 40-45 ° C. After the rubber is completely dissolved, the base composition in a homogeneous mixture is stored at ambient temperature. A crosslinkable base composition (referred to as CBR2) is obtained.
Next, an aliquot of 40.39 g of base composition CBR2 was stirred and at low temperature with 3.08 g MD ^Vi Q (OH) resin (E), 20.57 g peroxidized DCB and 20.57 g toluene. Add.
The resulting pressure sensitive adhesive composition is filled into a glass vial.

Example 8: Preparation of a pressure sensitive adhesive (PSA) composition according to the invention 3.03 g of MD ^Vi Q (OH) resin (E) with stirring and at low temperature into an aliquot of 40.62 g of base composition CBR2 1.05 g MDT (OH) resin (C), 0.63 g DCB peroxide and 20.60 g toluene.
The resulting pressure sensitive adhesive composition is packed into a glass vial.

Examples 9 and 10: Preparation of Pressure Sensitive Adhesive (PSA) Composition According to the Invention The procedure of Example 8 was followed except that the base composition CBR2, toluene, peroxidized DCB, MDT (OH) resin shown in Table 2 The amount (expressed in g) of (C) and MD ^Vi Q (OH) resin (E) was used.

Comparative Example 2: A pressure sensitive adhesive (PSA) composition having no MD ^Vi Q (OH) resin (E) was prepared by stirring into an aliquot of 39.93 g of base composition CBR2 obtained in Preparation Example 7 and At low temperature, 0.63 g of DCB peroxide and 20.55 g of toluene are added.
The resulting control pressure sensitive adhesive composition is filled into glass vials.

Manufacture of composite materials:
For Examples 1-10 and Comparative Examples 1 and 2, the mixture was already the required solids and already contained a peroxide catalyst. Therefore, these were applied as they were to a polyethylene terephthalate (PET) film having a thickness of 36 μm. The coating is carried out on a coating bench that makes it possible to obtain the desired coating thickness by adjusting the distance between the support (PET film) and the doctor blade. In this way, a coating having a thickness of 50 μm was carried out. Subsequently, the solvent is evaporated for 15 minutes under a fume hood, and radical crosslinking is initiated for 2 minutes in a 170 ° C. oven.
Thus, a PET film coated with the adhesive is obtained.
Subsequently, the adhesive was coated with polyethylene terephthalate that had been coated with 1 μm fluorosilicone and passed under a pressure of 25 kg / cm and then 45 kg / cm at a rate of 3 m / min to remove any bubbles. Protect with film. These aggregates are called “composites”.

Composition and film properties:
The properties of the polyethylene terephthalate film coated with the adhesive were demonstrated using the following test:

Test protocol
1. Tackiness:
ASTM D2979 “Probe Tack” standard method. The metal rod connected to the force sensor and the sample are brought into contact with each other at a speed of 1 cm / s. This contact time is 1 second. The force required to separate the rod from the adhesive coated film is measured and expressed in g / cm ² .

2. Peel strength:
ASTM D330A standard method. Adhesive coating film is applied to the metal plate. After a 1 minute standing time, the film is pulled away from the plate at an angle of 180 ° C. and a constant speed of 300 mm / min. The peel strength is measured with a sensor (expressed in g / cm).

3. Shear strength:
PSTC 107A and ASTM D6463A modified “Share Test” standard method. Bond the adhesive coated film to the metal plate. This is multiplied by a 1 kg weight over the maximum time set on the 7th. The time before the adhesive breakage of the adhesive was measured and expressed in time.

result

The above results show that when MD ^Vi Q resin is added at low temperatures,
It shows that peel strength (57%) is greatly increased; and that shear strength is significantly increased.

  By post-addition at low temperature, the addition of MDT (OH) resin (C) makes it possible to increase the tackiness of the PSA fairly significantly without reducing the peel strength.

Conclusion
^Allowing MD ^Vi Q resin to increase peel strength and shear strength;
・ Additional addition of MDT (OH) resin increases adhesion without reducing mechanical properties (peel strength)
Is shown.

  The above results show that it is possible to produce a PSA that is not sophisticated and has completely acceptable adhesive properties.

Claims (15)

A silicone composition comprising:
MQ (OH) type hydroxyl functional silicone resin A (where M: R ¹ R ² R ³ SiO _1/2 and Q (OH) :( OH) SiO _3/2 , R ¹ , R ² And R ³ are each independently
A linear or branched alkyl group having 1 to 8 carbon atoms, which may be substituted with one or more halogen atoms; and an aryl or alkylaryl group having 6 to 14 carbon atoms . )When,
Hydroxyl functional silicone rubber B;
A third component which is an MQ-type or MQ (OH) -type vinyl-functional silicone resin E, which is a D ^Vi and / or M ^Vi unit (where M: R ¹ R ² R ³ SiO _1/2 , M ^Vi : R ¹ R ² R ⁴ SiO _1/2 , D ^Vi : R ¹ R ⁴ SiO _2/2 , Q: SiO _4/2 and Q (OH) :( OH) SiO _3/2 ¹ , R ² and R ³ groups are each independently
A linear or branched alkyl group having 1 to 8 carbon atoms, optionally substituted with one or more halogen atoms; and an aryl or alkylaryl group having 6 to 14 carbon atoms; R ⁴ is a vinyl group. ). Hydroxyl-functional silicone resin C of the MDT (OH) or DT (OH) type (where M: R ¹ R ² R ³ SiO _1/2 , D: R ¹ R ² SiO _2/2 and T (OH): (OH) R ¹ SiO _2/2 wherein the R ¹ , R ² and R ³ groups are each independently
A linear or branched alkyl group having 1 to 8 carbon atoms, which may be substituted with one or more halogen atoms; and an aryl or alkylaryl group having 6 to 14 carbon atoms . The composition of claim 1, further comprising:   Composition according to claim 1 or 2, characterized in that it also comprises a condensation catalyst F and a neutralizing agent G.   The hydroxyl functional silicone resin A contains 40-80 mol% M units, 30-55 mol% Q units, 5-15 mol% Q (OH) units and 0.5 wt.% Based on the dry weight of the resin. 4. Composition according to any one of claims 1 to 3, characterized in that it comprises -4 wt% -OH hydroxyl units.   Composition according to any one of the preceding claims, characterized in that the hydroxyl-functional silicone rubber B is an α, ω-dihydroxyl polydialkylsiloxane having a molar mass ≥40000 g / mol. MQ or MQ (OH) type vinyl functional silicone resin E containing said D ^Vi and / or M ^Vi units comprises less than 5 wt% Vi groups and less than 0.4 wt% OH relative to the dry matter of the resin. The composition according to claim 1, wherein the composition is MD ^Vi Q (OH) or MM ^Vi Q (OH) resin.   The hydroxyl functional silicone resin C of the MDT (OH) or DT (OH) type, wherein the M, D and T units are methyl functional or phenyl functional units. The composition in any one of.   The hydroxyl functional silicone resin C is 15 to 30 mol% D units, 50 to 75 mol% T units, 0 to 20 mol% M units and 0.1 to 3 wt.% Based on the dry weight of the resin. A composition according to any one of claims 2 to 6, characterized in that it comprises% -OH hydroxyl units. Per 100% silicone active material on a dry / dry basis
20 to 80% by weight of hydroxyl functional silicone resin A;
20 to 80% by weight of hydroxyl functional silicone rubber B;
1 to 20% by weight vinyl functional silicone resin E; and 1 to 35% by weight hydroxyl functional silicone resin C
The composition according to claim 2, comprising:   10. Composition according to any one of claims 1 to 9, characterized in that it also contains one or more crosslinking agents. A method for producing a silicone pressure-sensitive adhesive composition, in an organic solvent S,
MQ (OH) type hydroxyl functional silicone resin A (where M: R ¹ R ² R ³ SiO _1/2 and Q (OH) :( OH) SiO _3/2 , R ¹ , R ² And R ³ are each independently
A linear or branched alkyl group having 1 to 8 carbon atoms, which may be substituted with one or more halogen atoms; and an aryl or alkylaryl group having 6 to 14 carbon atoms;
Selected from. )When,
Hydroxyl functional silicone rubber B;
MQ type or MQ (OH) type vinyl functional silicone resin E containing D ^Vi and / or M ^Vi units (where M: R ¹ R ² R ³ SiO _1/2 , M ^Vi : R ¹ R ² R ⁴ SiO _1/2 , D ^Vi : R ¹ R ⁴ SiO _2/2 , Q: SiO _4/2 and Q (OH) :( OH) SiO _3/2 , wherein R ¹ , R ² and R ³ groups are each independently
A linear or branched alkyl group having 1 to 8 carbon atoms, which may be substituted with one or more halogen atoms; and an aryl or alkylaryl group having 6 to 14 carbon atoms;
R ⁴ is a vinyl group. ). To the mixture, MDT (OH) or DT (OH) type hydroxyl functional silicone resin C (where M: R ¹ R ² R ³ SiO _1/2 , D: R ¹ R ² SiO _2/2 and T (OH) :( OH) R ¹ SiO _2/2 wherein the R ¹ , R ² and R ³ groups are each independently
A linear or branched alkyl group having 1 to 8 carbon atoms, which may be substituted with one or more halogen atoms; and an aryl or alkylaryl group having 6 to 14 carbon atoms . )
The method of claim 11, further comprising:   The method according to claim 11 or 12, wherein a condensation catalyst F and a neutralizing agent G are also added to the mixture.   The composite material provided with the support body at least covered with the crosslinked silicone composition in any one of Claims 1-10.   Use of the silicone composition according to any one of claims 1 to 10 for completely or partially covering the surface of a support for the purpose of imparting adhesive force on the support.