CN113308119B - Special addition type pad printing silica gel for electronic toy and preparation method thereof - Google Patents
Special addition type pad printing silica gel for electronic toy and preparation method thereof Download PDFInfo
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- CN113308119B CN113308119B CN202110645341.4A CN202110645341A CN113308119B CN 113308119 B CN113308119 B CN 113308119B CN 202110645341 A CN202110645341 A CN 202110645341A CN 113308119 B CN113308119 B CN 113308119B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to the technical field of silicon rubber products, in particular to an addition type pad printing silica gel special for an electronic toy and a preparation method thereof. The invention further increases the content of the reinforcing filler in the silica gel, so that the prepared pad printing silica gel has excellent mechanical property, and the flexibility of the prepared pad printing silica gel is increased by controlling the molecular weight of the vinyl silicone oil, so that the prepared pad printing silica gel has good curing property and the repeated use times are greatly increased.
Description
Technical Field
The invention relates to the technical field of silicon rubber products, in particular to an addition type pad printing silicon rubber special for an electronic toy and a preparation method thereof.
Background
The transfer printing silica gel is used for printing characters, figures and images on the surface of a silica gel product by transfer printing, and is widely applied to printing of PVC toys, electronic products, lamp decorations, plastic toys, electroplating products, trademarks, irregular patterns and the like.
The special addition type pad printing glue for the electronic toy mainly comprises five components: the performances of the vinyl silicone oil, the filler, the cross-linking agent (hydrogen-containing silicone oil), the catalyst and the inhibitor depend on a plurality of factors, such as the content and the molecular weight of vinyl in the vinyl silicone oil, the content and the molecular weight of hydrogen in the hydrogen-containing silicone oil in the cross-linking agent, the processing degree of hydroxyl in the filler, the added inhibitor, modifier and other components. In the existing special addition type pad printing glue for the electronic toy, in order to enhance the performance of a certain aspect, defects of other aspects are often brought, for example, the storage time and the mechanical strength of the addition type electronic pad printing glue are greatly reduced by adding additives for improving the antistatic property of the pad printing glue after curing; the cross-linking points between molecules are increased to improve the mechanical strength, but the viscosity of the polymer used is increased. Therefore, how to prepare the pad printing glue for the electronic toy, which has the advantages of more pad printing times, high tensile strength, high elongation, high tearing strength and good wear resistance, becomes a problem to be solved urgently.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the special addition type pad printing silica gel for the electronic toy and the preparation method thereof.
The technical purpose of the invention is realized by the following technical scheme that the special addition type pad printing silica gel for the electronic toy comprises a component A and a component B, wherein the components comprise the following components in percentage by weight:
component A
B component
The base adhesive is prepared from a reinforcing filler and vinyl-terminated silicone oil, and the surface of the reinforcing filler is pretreated by a mixture of silazane and vinyl silazane.
Further, in the base rubber, the mass ratio of the reinforcing filler to the vinyl-terminated silicone oil is 30-40.
In the present invention, the ratio by mass of the silazane, the vinyl silazane to the reinforcing filler is 15 to 25.
Further, in the reinforcing filler, the content of Si-OH is less than 3.0/nm 2 。
Further, the reinforcing filler is precipitated silica.
In the invention, in the base rubber, the number average molecular weight of the vinyl-terminated silicone oil is 55000-62700.
In the invention, the viscosity of the vinyl-terminated silicone oil is 10000 mPa.s, and the vinyl content is 0.08-0.12%.
Further, in the component A, the terminal vinyl silicone oil comprises a first terminal vinyl silicone oil and a second terminal vinyl silicone oil, and the ratio of the first terminal vinyl silicone oil to the second terminal vinyl silicone oil is 1:1.
Further, the first terminal vinyl silicone oil has a viscosity of 1000mPa · s, a molecular weight of 28000, and a vinyl content of 0.18 to 0.26%, and the second terminal vinyl silicone oil has a viscosity of 5000mPa · s, a molecular weight of 49500, and a vinyl content of 0.10 to 0.13%.
The invention also aims to provide a preparation method of the special addition type pad printing silica gel for the electronic toy, which comprises the following steps:
(1) Preparing base rubber: putting the reinforcing filler subjected to surface pretreatment and the vinyl-terminated silicone oil into a kneading machine, stirring to prepare a base polymer, controlling the temperature to be 180-220 ℃, performing vacuum reduction on the base polymer, and processing the reduced base polymer by a three-roll machine to prepare a base adhesive;
(2) Preparing a component A: adding the vinyl-terminated silicone oil, the polydimethylsiloxane and the platinum complex catalyst into the base adhesive, uniformly stirring, and then defoaming in vacuum;
(3) Preparing a component B: mixing and uniformly stirring hydrogen-terminated polydimethylsiloxane, terminal hydrogen-containing silicone oil, an antistatic agent, tetramethyl tetravinylcyclotetrasiloxane and polydimethylsiloxane;
(4) And (3) transfer printing silica gel forming: and (3) uniformly mixing the component A and the component B, performing vacuum defoaming, then performing reverse molding and curing, and preparing the transfer printing rubber head after the curing is complete.
The invention has the following beneficial effects:
(1) The mixture of silazane and vinyl silazane is adopted to carry out surface pretreatment on the reinforcing filler, control the Si-OH content of the reinforcing filler and increase the affinity of the reinforcing filler to oil, so that the content of the reinforcing filler in the pad printing silica gel can be increased, and the mechanical properties of the product, such as tearing strength, and the like, are greatly improved;
(2) The flexibility of the terminal vinyl silicone oil is increased by controlling the molecular weight, vinyl content and the like of the terminal vinyl silicone oil in the component A, so that the prepared transfer printing silica gel has good curing property and the repeated use times are greatly increased.
Detailed Description
The present invention is described in further detail below with reference to examples, which are intended to facilitate the understanding of the present invention and are not intended to limit the present invention in any way. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, this phrase shall render the claim closed except for the materials described except for those materials normally associated therewith. When the phrase "consisting of …" appears in a clause of the subject of the claims rather than immediately after the subject matter, it defines only the elements described in that clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
Example 1
The component A comprises: 100 parts of base rubber, 2 parts of vinyl-terminated silicone oil, 5 parts of polydimethylsiloxane and 0.2 part of platinum complex catalyst; and B component: 9 parts of hydrogen-terminated polydimethylsiloxane, 35 parts of hydrogen-containing silicone oil in the terminal, 20 parts of antistatic agent, 1.8 parts of tetramethyl tetravinylcyclotetrasiloxane and 33 parts of polydimethylsiloxane.
Wherein the mass ratio of the component A to the component B is 10.
The base rubber is prepared from a reinforcing filler subjected to surface pretreatment and terminal vinyl silicone oil, wherein the mass ratio of the reinforcing filler to the terminal vinyl silicone oil is 35:65.
wherein, the reinforcing filler is precipitated silica, and the precipitated silica is subjected to surface pretreatment by adopting a mixture of silazane and vinyl silazane. The surface pretreatment is to put the silicon dioxide obtained by the precipitation method into a closed container, then put a mixture of silazane and vinyl silazane, and close the container after the feeding is finished.
Wherein the ratio of silazane, vinyl silazane, and precipitated silica is 20.
Wherein the content of Si-OH in the reinforcing filler is less than 3.0/nm 2 . The Si-OH content of the reinforcing filler is controlled at 3.0 pieces/nm 2 And the affinity of the reinforcing filler can be effectively changed, so that the hydrophilic property of the reinforcing filler is changed into the hydrophobic property, and the addition amount of the reinforcing filler in the transfer printing silica gel can be increased.
Wherein, one of the synthetic raw materials of the base adhesive, the viscosity of the vinyl-terminated silicone oil is 10000 mPa.s, the molecular weight is controlled to 55000, and the vinyl content is 0.08-0.12%. The molecular weight of the vinyl silicone oil is controlled in a certain range, so that the prepared pad printing silica gel has good curing property, and the repeated use times are greatly increased.
In the component A, the terminal vinyl silicone oil comprises a first terminal vinyl silicone oil and a second terminal vinyl silicone oil, and the ratio of the first terminal vinyl silicone oil to the second terminal vinyl silicone oil is 1:1.
Wherein the first terminal vinyl silicone oil has a viscosity of 1000 mPas, a molecular weight of 28000, and a vinyl content of 0.18-0.26%.
Wherein the viscosity of the second terminal vinyl silicone oil is 5000 mPas, the molecular weight is 49500, and the vinyl content is 0.10-0.13%.
Wherein the concentration of the platinum complex catalyst was 10ppm.
Wherein, in the component A, the viscosity of the polydimethylsiloxane is 10 mPas.
Wherein, in the component B, the hydrogen content of the hydrogen-terminated polydimethylsiloxane is 0.2 percent.
In the component B, the hydrogen content of the hydrogen-containing silicone oil in the terminal is 0.45%, the viscosity is 40mPa & s, and the component B is selected from XJY-711 of Xinjiayi new material Co.
Wherein, in the component B, the antistatic agent is KD-1 antistatic agent.
Wherein, in the component B, the viscosity of the polydimethylsiloxane is 10 mPas.
In this example, the preparation method was as follows:
(1) Preparing base rubber: the surface pretreatment is carried out on filler precipitation method silicon dioxide by using a mixture of silazane and vinyl silazane, the treatment time exceeds 7 days, after the treatment is finished, the precipitation method silicon dioxide and terminal vinyl silicone oil are put into a kneading machine to be stirred to prepare a base polymer, the temperature is controlled to be 180 ℃, the vacuum degree is-0.095 MPa, the base polymer is subjected to low removal, small molecular substances are removed, macromolecules are generated by polymerization, and the base polymer after the low removal is processed by a three-roll machine to prepare base rubber;
(2) Preparing a component A: adding first terminal vinyl silicone oil, second terminal vinyl silicone oil, polydimethylsiloxane and platinum complex catalyst into the base rubber, uniformly stirring, and then defoaming in vacuum under-0.095 MPa to discharge bubbles in the components;
(3) Preparing a component B: mixing and uniformly stirring hydrogen-terminated polydimethylsiloxane, terminal hydrogen-containing silicone oil, KD-1 antistatic agent, tetramethyl tetravinylcyclotetrasiloxane and polydimethylsiloxane;
(4) And (3) transfer printing silica gel forming: and uniformly mixing the component A and the component B, performing vacuum defoaming, then performing reverse molding and curing, and preparing the pad printing rubber head after curing is completed.
Example 2
The present embodiment is different from embodiment 1 in that:
the component A comprises: 80 parts of base rubber, 6 parts of vinyl-terminated silicone oil, 10 parts of polydimethylsiloxane and 0.1 part of platinum complex catalyst; and the component B comprises: 6 parts of hydrogen-terminated polydimethylsiloxane, 30 parts of hydrogen-containing silicone oil in the terminal, 15 parts of antistatic agent, 1.5 parts of tetramethyl tetravinylcyclotetrasiloxane and 30 parts of polydimethylsiloxane.
Wherein the mass ratio of the component A to the component B is 8:1.
Wherein the mass ratio of the reinforcing filler to the vinyl-terminated silicone oil is 30:60.
wherein the ratio of silazane, vinyl silazane, and precipitated silica is 15.5.
Wherein, the molecular weight of the vinyl-terminated silicone oil which is one of the synthetic raw materials of the base rubber is controlled at 59000.
The preparation method of this example differs from that of example 1 in that: in the step (1), the temperature is controlled to be 200 ℃.
Example 3
The present embodiment is different from embodiment 1 in that:
the component A comprises: 120 parts of base rubber, 10 parts of vinyl-terminated silicone oil, 15 parts of polydimethylsiloxane and 0.3 part of platinum complex catalyst; and B component: 12 parts of hydrogen-terminated polydimethylsiloxane, 40 parts of hydrogen-containing silicone oil in the terminal, 25 parts of antistatic agent, 2.0 parts of tetramethyl tetravinylcyclotetrasiloxane and 36 parts of polydimethylsiloxane.
Wherein the mass ratio of the component A to the component B is 12.
Wherein the mass ratio of the reinforcing filler to the vinyl-terminated silicone oil is 40:70.
wherein the ratio of silazane, vinyl silazane, and precipitated silica is 25.
Wherein, the molecular weight of the vinyl-terminated silicone oil, one of the synthetic raw materials of the base rubber, is controlled to be 62700.
The preparation method of this example differs from that of example 1 in that: in the step (1), the temperature is controlled to be 220 ℃.
The special pad printing silica gel for the electronic toy, which is prepared by the invention, can be continuously used at the temperature of below 140 ℃, can be baked in an oven at the temperature of 200 ℃ for 3 months without softening the colloid and cracking, and can be exposed outdoors for more than 6 months without cracks, wherein the product performance and the commercial products (electrostatic glue) of the pad printing silica gel prepared in the embodiment 1 are shown in the following table:
the foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is conceivable, and the examples presented herein demonstrate the results of applicants' actual experiments. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (6)
1. The special addition type pad printing silica gel for the electronic toy comprises a component A and a component B, and is characterized in that the components comprise the following components in percentage by weight:
component A
80-120 parts of base rubber
2-10 parts of vinyl-terminated silicone oil
5-15 parts of polydimethylsiloxane
0.1-0.3 part of platinum complex catalyst
B component
6-12 parts of hydrogen-terminated polydimethylsiloxane
30-40 parts of hydrogen-containing silicone oil in terminal
15-25 parts of antistatic agent
1.5-2.0 parts of tetramethyl tetravinylcyclotetrasiloxane
30-36 parts of polydimethylsiloxane
The base adhesive is prepared from a reinforcing filler and vinyl-terminated silicone oil, and the surface of the reinforcing filler is pretreated by a mixture of silazane and vinyl silazane; the mass ratio of the silazane to the vinyl silazane to the reinforcing filler is 15-25, 95-105, and the content of Si-OH in the reinforcing filler is less than 3.0 per nm 2 (ii) a The number average molecular weight of the vinyl-terminated silicone oil is 55000-62700; the reinforcing filler is precipitated silica; the hydrogen content of the hydrogen-containing silicone oil in the terminal is 0.45%, the viscosity is 40mPa & s, and the hydrogen-containing silicone oil is selected from Jiangxi Xinjiayi new material Co., ltd., brand XJY-711;
the preparation method comprises the following steps:
(1) Preparing base rubber: putting the reinforcing filler subjected to surface pretreatment and the terminal vinyl silicone oil into a kneading machine, stirring to prepare a base polymer, controlling the temperature to be 180-220 ℃, performing vacuum reduction on the base polymer, and processing the reduced base polymer by a three-roll machine to prepare a base rubber;
(2) Preparing a component A: adding the vinyl-terminated silicone oil, the polydimethylsiloxane and the platinum complex catalyst into the base adhesive, uniformly stirring, and then defoaming in vacuum;
(3) Preparing a component B: mixing and uniformly stirring hydrogen-terminated polydimethylsiloxane, terminal hydrogen-containing silicone oil, an antistatic agent, tetramethyl tetravinylcyclotetrasiloxane and polydimethylsiloxane;
(4) And (3) transfer printing silica gel forming: and (3) uniformly mixing the component A and the component B, performing vacuum defoaming, then performing reverse molding and curing, and preparing the transfer printing silica gel after the curing is complete.
2. The special addition type pad printing silica gel for the electronic toy as claimed in claim 1, wherein the mass ratio of the reinforcing filler to the vinyl-terminated silicone oil in the base gel is 30-40.
3. The special addition type pad printing silica gel for electronic toys as claimed in claim 1, wherein the viscosity of the vinyl-terminated silicone oil in the base gel is 10000mPa · s, and the vinyl content is 0.08-0.12%.
4. The special addition type transfer printing silicone rubber for electronic toys as claimed in claim 1, wherein in said component A, said terminal vinyl silicone oil comprises a first terminal vinyl silicone oil and a second terminal vinyl silicone oil, and the ratio of said first terminal vinyl silicone oil to said second terminal vinyl silicone oil is 1:1.
5. The addition type pad printing silica gel special for electronic toys according to claim 4, wherein the viscosity of the first terminal vinyl silicone oil is 1000mPa s, the molecular weight is 28000, the vinyl content is 0.18-0.26%, the viscosity of the second terminal vinyl silicone oil is 5000mPa s, the molecular weight is 49500, and the vinyl content is 0.10-0.13%.
6. The method for preparing the special addition type pad printing silica gel for the electronic toy according to claim 1, which is characterized by comprising the following steps:
(1) Preparing base rubber: putting the reinforcing filler subjected to surface pretreatment and the vinyl-terminated silicone oil into a kneading machine, stirring to prepare a base polymer, controlling the temperature to be 180-220 ℃, performing vacuum reduction on the base polymer, and processing the reduced base polymer by a three-roll machine to prepare a base adhesive;
(2) Preparing a component A: adding the vinyl-terminated silicone oil, the polydimethylsiloxane and the platinum complex catalyst into the base adhesive, uniformly stirring, and then defoaming in vacuum;
(3) Preparing a component B: mixing and uniformly stirring hydrogen-terminated polydimethylsiloxane, terminal hydrogen-containing silicone oil, an antistatic agent, tetramethyl tetravinylcyclotetrasiloxane and polydimethylsiloxane;
(4) And (3) transfer printing silica gel forming: and (3) uniformly mixing the component A and the component B, performing vacuum defoaming, then performing reverse molding and curing, and preparing the pad printing silica gel after curing is completed.
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| CN202110645341.4A CN113308119B (en) | 2021-06-10 | 2021-06-10 | Special addition type pad printing silica gel for electronic toy and preparation method thereof |
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| CN202110645341.4A CN113308119B (en) | 2021-06-10 | 2021-06-10 | Special addition type pad printing silica gel for electronic toy and preparation method thereof |
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| CN112159595A (en) * | 2020-10-16 | 2021-01-01 | 深圳市久和丝印器材有限公司 | Rubber head for pad printing of different types of hand surface plate glass and preparation method thereof |
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| CN112898782B (en) * | 2021-01-20 | 2022-11-11 | 东莞市正安有机硅科技有限公司 | Liquid silicone rubber for pad printing rubber head and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112159595A (en) * | 2020-10-16 | 2021-01-01 | 深圳市久和丝印器材有限公司 | Rubber head for pad printing of different types of hand surface plate glass and preparation method thereof |
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