CN103013126A - Baby rubber products and composition for forming the same - Google Patents
Baby rubber products and composition for forming the same Download PDFInfo
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- CN103013126A CN103013126A CN 201210351837 CN201210351837A CN103013126A CN 103013126 A CN103013126 A CN 103013126A CN 201210351837 CN201210351837 CN 201210351837 CN 201210351837 A CN201210351837 A CN 201210351837A CN 103013126 A CN103013126 A CN 103013126A
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Abstract
The invention provides a nipple for a feeding bottle and a baby pacifier, which consist of silicon rubbers which are low in hardness, high in tensility, tensile strength and tear strength, and good in rubber elasticity without sticky rubber touch feeling. A short-chain organic organopolysiloxane which contains alkenyl and is at the liquid state at the room temperature and an organic silicon resin containing the alkenyl are composed to form an addition curable silicone rubber composition and the addition curable silicon rubber composition is heated and cured.
Description
Technical field
The present invention relates to rubber product forming composition for baby, it is 10～30 by giving the soft hardness that (utilizing sclerometer A(Durometer A, Shore scleroscope) records) the addition curing rubber composition of cured article (silicon rubber) consist of.More specifically, relate to molding composition and said composition is heating and curing the lactation sucker for drinking purposes that forms and child with rubber items for baby such as Pacifiers, even the hardness that described molding composition can form after solidifying is soft, tear strength is also high, the surface does not have the silicon rubber of sticky feeling, in particular for rubber items for baby such as moulding lactation sucker for drinking purposes and Pacifiers for baby.
Background technology
Silicon rubber from thermotolerance, winter hardiness, security, outward appearance good (transparency), sense of touch is good and the good aspect of weather resistance is considered, is widely used as the moulding child with the material of toy or tableware, toothbrush etc., especially lactation sucker for drinking purposes or Pacifier for baby.Especially the rubber composition of addition reaction curing is considered from the by product that is decomposed to form, the especially security aspect that do not produce organo-peroxide as organic peroxide curing type, is suitable for such use.But, reach the intensity that can be applied to these lactation sucker for drinking purposes or Pacifier for baby in order to make silicon rubber, must cooperate enhancement silicon-dioxide, but have the such problem of hardness rising when adding enhancement silicon-dioxide.
At present, the hardness of the lactation sucker for drinking purposes of widely used organosilicon system (sclerometer A) is 30～50, in order to seek the variation of its design, perhaps is used for the weak child of suction, the lactation sucker for drinking purposes of expectation soft.But when the amount of enhancement silicon-dioxide was reduced, destrengthening then when taking out forming composition from mould after moulding, be full of cracks occurs in rubber, or rubber was cut off easily in use.In addition, do not make enhancement silicon-dioxide reduce, will addition-crosslinked balance destroy and become soft the time, become and have rubber that elastic force weakens or the rubber of surfaces of tacky, as lactation sucker for drinking purposes or Pacifier for baby, for feeling the nipple of discomfort.
Need to prove, as the prior art relevant with the present invention, can enumerate following document.
[prior art document]
[patent documentation]
[patent documentation 1] TOHKEMY 2003-321609 communique
Summary of the invention
The problem that invention will solve
The present invention is the invention of finishing in order to improve above-mentioned situation, its purpose is, the rubber product forming for baby rubber items for baby such as the lactation sucker for drinking purposes that forms and Pacifier for baby that are heating and curing with composition and with said composition are provided, described rubber product forming for baby with composition by giving high for soft, high stretch and tensile strength and tear strength and having good caoutchouc elasticity, do not have the addition curing rubber composition of cured article (silicon rubber) of the rubber sense of touch of viscosity sense to consist of.
Be used for solving the means of problem
The inventor concentrates on studies in order to achieve the above object, found that, by will be at room temperature making up for the silicone resin that contains thiazolinyl short chain organopolysiloxane and contain thiazolinyl of liquid, obtain giving for soft and have caoutchouc elasticity, have the addition curing rubber composition of the silicon rubber of suitable sense of touch as lactation sucker for drinking purposes and Pacifier for baby, until finished the present invention.
Therefore, the invention provides rubber item for baby and the rubber product forming composition for baby shown in following.
Rubber item for baby, it is used for the baby suckes in mouth and stings or suck, and is characterised in that, and the hardness of utilizing sclerometer A sclerometer to record is 10～30, and it comprises the cured article of addition curing rubber composition, and described addition curing rubber composition contains:
(A) containing at least 2 thiazolinyl, mean polymerisation degree with silicon atom bonding in 1 molecule is below 1,500, at room temperature is the organopolysiloxane of liquid: 100 mass parts,
(B) containing 0～5 thiazolinyl, mean polymerisation degree with silicon atom bonding in 1 molecule is the gluey organopolysiloxane of making a living under the room temperature more than 2,000: 0～50 mass parts,
(C) do not have addition reactivity functional group, mean polymerisation degree is the organopolysiloxane below 300: 0～50 mass parts,
(D) with R
3SiO
1/2Unit (in the formula, R is the monovalence alkyl that does not replace or replace) and SiO
2The unit is main component, R
3SiO
1/2Unit and SiO
2Mol ratio [the R of unit
3SiO
1/2/ SiO
2] be 0.5～1.5 and contain 5 * 10
-3～1 * 10
-4The resinous material multipolymer of the vinyl of mol/g: 0.1～20 mass parts,
(E) contain at least 2 organic hydrogen polysiloxanes with the hydrogen atom of silicon atom bonding in 1 molecule: total 100 mass parts with respect to (A)～(D) composition are 0.2～20 mass parts,
(F) specific surface area according to the BET method is 150m
2The aerosil that/g is above: total 100 mass parts with respect to (A)～(D) composition are 10～50 mass parts,
(G) addition reaction catalyst: catalytic amount.
Such as [1] described rubber item for baby, wherein, (B) use level of composition is 5～50 mass parts with respect to 100 mass parts (A) composition.
Such as [1] described rubber item for baby, wherein, (C) use level of composition is 5～50 mass parts with respect to 100 mass parts (A) composition.
Such as [1] described rubber item for baby, wherein, the viscosity under 25 ℃ is the scope of 50～5,000Pas, is used for liquid injection molding.
Such as [1] described rubber item for baby, tensile strength is more than the 3.0MPa, and elongation at break is more than 400%.
Such as [1] described rubber item for baby, tear strength is more than the 10kN/m.
Such as each described rubber item for baby in [1]～[6], it is the lactation sucker for drinking purposes.
Such as each described rubber item for baby in [1]～[6], it is Pacifier for baby.
Rubber product forming composition for baby, it is the molding composition of sucking the rubber item for baby of stinging or sucking for the baby in mouth, be characterised in that, it comprises the addition reaction curable silicone rubber composition, it is 10～30 cured article that described addition reaction curable silicone rubber composition is given according to the scleroscopic hardness of sclerometer A by curing, and contains:
(A) containing at least 2 thiazolinyl, mean polymerisation degree with silicon atom bonding in 1 molecule is below 1,500, at room temperature is the organopolysiloxane of liquid: 100 mass parts,
(B) containing 0～5 thiazolinyl, mean polymerisation degree with silicon atom bonding in 1 molecule is the gluey organopolysiloxane of making a living under the room temperature more than 2,000: 0～50 mass parts,
(C) do not have addition reactivity functional group, mean polymerisation degree is the organopolysiloxane below 300: 0～50 mass parts,
(D) with R
3SiO
1/2Unit (in the formula, R is the monovalence alkyl that does not replace or replace) and SiO
2The unit is main component, R
3SiO
1/2Unit and SiO
2Mol ratio [the R of unit
3SiO
1/2/ SiO
2] be 0.5～1.5 and contain 5 * 10
-3～1 * 10
-4The resinous material multipolymer of the vinyl of mol/g: 0.1～20 mass parts,
(E) contain at least 2 organic hydrogen polysiloxanes with the hydrogen atom of silicon atom bonding in 1 molecule: total 100 mass parts with respect to (A)～(D) composition are 0.2～20 mass parts,
(F) specific surface area according to the BET method is 150m
2The aerosil that/g is above: total 100 mass parts with respect to (A)～(D) composition are 10～50 mass parts,
(G) addition reaction catalyst: catalytic amount.
Such as [9] described molding composition, wherein, (B) use level of composition is 5～50 mass parts with respect to 100 mass parts (A) composition.
Such as [9] described molding composition, wherein, (C) use level of composition is 5～50 mass parts with respect to 100 mass parts (A) composition.
Such as [9] described molding composition, wherein, the viscosity under 25 ℃ is the scope of 50～5,000Pas, is used for liquid injection molding.
Such as [9] described molding composition, the tensile strength of cured article is more than the 3.0MPa, and elongation at break is more than 400%.
Such as [9] described molding composition, wherein, the tear strength of cured article is more than the 10kN/m.
Such as each described molding composition in [9]～[14], wherein, rubber item for baby is the lactation sucker for drinking purposes.
Such as each described molding composition in [9]～[14], wherein, rubber item for baby is Pacifier for baby.
The effect of invention
According to the present invention, the combination of the specified quantitative by above-mentioned (A)～(G) composition can provide the rubber product forming composition for baby of giving soft and almost not having surface viscosity, silicon rubber cured article that tear strength is high.In addition, can provide soft by the cured article of said composition and almost not have the lactation sucker for drinking purposes of surface viscosity, silicon rubber that tear strength is high or the rubber item for baby such as Pacifier for baby.
Embodiment
Below the rubber product forming for baby that comprises addition curing rubber composition of the present invention is described in further detail with composition.
At first, contain at least 2 thiazolinyl, mean polymerisation degree with silicon atom bonding in 1 molecule as (A) composition and be below 1,500, room temperature (25 ℃, below identical.) lower to liquid organopolysiloxane is the host (base polymer) of this composition, as this organopolysiloxane, can use by shown in the following average composition formula I, at room temperature be the organopolysiloxane of liquid.
R
1 aSiO
(4-a)/2 …(Ⅰ)
(in the formula, R
1For the carbonatoms that is same to each other or different to each other is 1～10, preferred 1～8 not replacement or replaces the monovalence alkyl, a is 1.5～2.8, the positive number of preferred 1.8～2.5, more preferably 1.95～2.05 scope.)
At this, as above-mentioned by R
1Shown and carbonatoms silicon atom bonding are 1～10, preferred 1～8 the monovalence alkyl that does not replace or replace, and can enumerate: the alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, cyclohexyl, octyl group, nonyl, decyl; The aryl such as phenyl, tolyl, xylyl, naphthyl; The aralkyl such as benzyl, phenylethyl, phenyl propyl; The thiazolinyls such as vinyl, allyl group, propenyl, pseudoallyl, butenyl, hexenyl, cyclohexenyl, octenyl, or the part or all of hydrogen atom of these groups group, such as chloromethyl, chloropropyl, bromotrifluoromethane, trifluoro propyl, cyano ethyl etc. that have been replaced by the halogen atoms such as fluorine, bromine, chlorine, cyano group etc., preferred all R
1Be methyl more than 90 % by mole.
In addition, R
1In at least 2 for thiazolinyl be necessary (preferred carbonatoms is 2～8, more preferably 2～6, be particularly preferably vinyl.)。
Need to prove, the content of thiazolinyl is 1.0 * 10 in organopolysiloxane
-6Mol/g～5.0 * 10
-4Mol/g is particularly preferably 1.0 * 10
-5Mol/g～2.0 * 10
-4Mol/g.The amount of thiazolinyl is less than 1.0 * 10
-6During mol/g, rubber hardness is crossed low and is become gel sometimes, in addition, when its greater than 5.0 * 10
-4During mol/g, cross-linking density excessively raises, and sometimes becomes the high rubber of hardness.This thiazolinyl can with the silicon atom bonding of molecule chain end, also can with molecular chain silicon atom bonding midway, can also be bonded to both.
The structure of this organopolysiloxane has the straight chain structure that molecular chain two ends are made of two organo-siloxane repeating units by three organic siloxy-end-blockings, main chain basically, partly can be the structure of side chain shape, ring texture etc.
About molecular weight, mean polymerisation degree (weight average degree of polymerization, following identical.) be below 1,500, be generally 100～1,500, preferred 150～1,100.When it is lower than 100, sometimes can not obtain sufficient rubber sense, when it is higher than at 1,500 o'clock, viscosity raises, the moulding difficult.At this, molecular weight or the polymerization degree can be used as such as the weight-average molecular weight of the polystyrene conversion in the gel permeation chromatography take toluene as developing solvent (GPC) analysis or weight average degree of polymerization etc. and obtain (following identical.)。
Secondly, having 0～5 thiazolinyl, mean polymerisation degree (weight average degree of polymerization) with silicon atom bonding in 1 molecule as (B) composition is 2, make a living more than 000, under room temperature (25 ℃) organopolysiloxane of glue (the on-liquid shape that does not namely have auto flowability) can use by the organopolysiloxane shown in the following average composition formula II.
R
2 bSiO
(4-b)/2 …(Ⅱ)
(in the formula, R
2For the carbonatoms that is same to each other or different to each other is 1～10, preferred 1～8 not replacement or replaces the monovalence alkyl, b is 1.8～2.5, the positive number of preferred 1.9～2.1, more preferably 1.98～2.01 scope.)
At this, as by above-mentioned R
2Shown and carbonatoms silicon atom bonding are 1～10, preferred 1～8 the monovalence alkyl that does not replace or replace, with above-mentioned R
1Equally, can enumerate: the alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, cyclohexyl, octyl group, nonyl, decyl; The aryl such as phenyl, tolyl, xylyl, naphthyl; The aralkyl such as benzyl, phenylethyl, phenyl propyl; The thiazolinyls such as vinyl, allyl group, propenyl, pseudoallyl, butenyl, hexenyl, cyclohexenyl, octenyl, or the part or all of hydrogen atom of these groups group, such as chloromethyl, chloropropyl, bromotrifluoromethane, trifluoro propyl, cyano ethyl etc. that have been replaced by the halogen atoms such as fluorine, bromine, chlorine, cyano group etc., preferred all R
2Be methyl more than 90 % by mole.
In addition, at R
2In can contain thiazolinyl (preferred carbonatoms is 2～8 thiazolinyl, more preferably 2～6, be particularly preferably vinyl.), also can not contain thiazolinyl, when containing thiazolinyl, the content of this thiazolinyl is more than 1 below 5 in 1 molecule, and is preferably 0.0002mol/g following (0～2 * 10
-4Mol/g), be particularly preferably 0.00005mol/g following (5 * 10
-8～5 * 10
-5Mol/g).The amount of thiazolinyl is during greater than 0.0002mol/g, and rubber hardness raises sometimes.This thiazolinyl can with the silicon atom bonding of molecule chain end, also can with molecular chain silicon atom bonding midway, can also be bonded to both.
The structure of this organopolysiloxane, same with aforementioned (A) composition, basically have the straight chain structure that molecular chain two ends are made of two organo-siloxane repeating units by three organic siloxy-end-blockings, main chain, partly can be the structure of side chain shape, ring texture etc.About molecular weight, for mean polymerisation degree is (to be generally 2 more than 2,000, about 000～100,000), the material of glue (the on-liquid shape that does not namely have auto flowability) of under room temperature (25 ℃), making a living, preferred more than 3,000 (3, about 000～80,000) material.Mean polymerisation degree is lower than at 2,000 o'clock, not only can not obtain sufficient rubber sense, and generation is clamminess on the surface.
(B) composition is any composition that can cooperate as required, with respect to 100 mass parts (A) composition, is 0～50 mass parts, preferred 5～50 mass parts, more preferably 10～40 mass parts, the further scope of preferred 10～30 mass parts.When this use level surpassed 50 mass parts, the viscosity of composition was high, the moulding difficult.
As (C) composition do not have addition reactivity functional group hydrogen atom (SiH yl) functional group that consist of, that can participate in the hydrosilylation addition reaction of the thiazolinyl such as vinyl and silicon atom bonding (namely by), mean polymerisation degree is the organopolysiloxane below 300, can illustration by (preferably without the functionality) diorganopolysiloxanecompositions of the straight chain shape shown in the following logical formula III.
[changing 1]
(in the formula, R
4For the carbonatoms that is same to each other or different to each other is 1～10, preferred carbonatoms 1～6 do not replace or halogen replaces, alkyl or aryl, for example can enumerate: methyl, ethyl, propyl group, butyl, hexyl, cyclohexyl, phenyl, 3,3,3-trifluoro propyl etc., wherein, preferable methyl, phenyl, 3,3, the 3-trifluoro propyl is particularly preferably methyl.R
4Can be identical or different, preferred all R
4Be methyl more than 90 % by mole.N be below 300 (namely 0～300) integer, be preferably 2～250 integer.)
As (C) composition, except above-mentioned straight chain shape without the functionality diorganopolysiloxanecompositions, even contain the also no problem without the functionality organopolysiloxane of ring texture or branched structure.
Need to prove, mean polymerisation degree (or n of above-mentioned formula) surpasses at 300 o'clock, even also be clamminess in the generation of the surface of silicon rubber cured article with a small amount of cooperation.
(C) any composition of composition for cooperating as required, its use level is 0～50 mass parts with respect to 100 mass parts (A) composition, preferred 5～50 mass parts, more preferably 10～40 mass parts, further preferred 10～30 mass parts.When this use level surpassed 50 mass parts, the rubber physical property of cured article significantly reduced.
For soft and the material that cooperates in order to give the physical propertys such as high-tear strength, high tensile, high extensibility, for containing R in the cured article of this composition as the resinous material multipolymer of (D) composition
3SiO
1Unit/2 and SiO2 unit are as silicone resin main component, so-called tridimensional network.At this, R is the monovalence alkyl that does not replace or replace, preferred carbonatoms is 1～10, particularly preferably 1～8 alkyl, as by the monovalence alkyl shown in the R, can enumerate: the alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, cyclohexyl, octyl group, nonyl, decyl; The aryl such as phenyl, tolyl, xylyl, naphthyl; The aralkyl such as benzyl, phenylethyl, phenyl propyl; The thiazolinyls such as vinyl, allyl group, propenyl, pseudoallyl, butenyl, hexenyl, cyclohexenyl, octenyl, or the group that replaced by the halogen atoms such as fluorine, bromine, chlorine, cyano group etc. of the part or all of hydrogen atom of these groups, such as chloromethyl, chloropropyl, bromotrifluoromethane, trifluoro propyl, cyano ethyl etc.
Resinous material multipolymer as (D) composition can be for only comprising above-mentioned R
3SiO
1/2Unit and SiO
2The material of unit, in addition, as required, with respect to the total copolymer quality, with its total quantifier, can be below 50%, preferred scope below 40% contains R
2SiO
2/2Unit or RSiO
3/2Unit (R as mentioned above), but R
3SiO
1/2Unit and SiO
2Mol ratio [the R of unit
3SiO
1/2/ SiO
2] be 0.5～1.5, be in particular 0.5～1.3rd, necessary.This mol ratio was less than 0.5 o'clock, and the hardness of cured article raises, and the consistency reduction, cooperated difficult, and it can not get sufficient intensity greater than 1.5 o'clock.
In addition, the resinous material multipolymer as (D) composition contains 5 * 10
-3～1 * 10
-4Mol/g, contain 3 * 10 especially
-3～2 * 10
-4The vinyl of mol/g is necessary.Contents of ethylene is greater than 5 * 10
-3During mol/g, rubber is hard and become fragile, when its less than 1 * 10
-4During mol/g, can not obtain sufficient intensity.
Aspect Reinforced Rubber stably, the weight-average molecular weight of above-mentioned resinous material multipolymer is preferably 400～100, and 000, be particularly preferably 500～30,000, especially be preferably about 800～8,000.When weight-average molecular weight is too small, sometimes can not give full play to the reinforced effects of rubber (cured article), when it is excessive, sometimes can not stably make.
Need to prove, above-mentioned resinous material multipolymer usually can by with suitable chlorosilane, organoalkoxysilane with well-known method in this technical field be hydrolyzed, condensation makes.
The use level of these resinous material multipolymers with respect to 100 mass parts (A) composition, is 0.1～20 mass parts, particularly preferably 1～10 mass parts.When the use level of resinous material multipolymer is very few, can not fully give the characteristics such as soft and high-tear strength, high tensile, high extensibility, when it surpasses 20 mass parts, the excessive hardening of rubber.
(E) composition be have in 1 molecule at least 2, preferred more than 3 with the organic hydrogen polysiloxanes of the hydrogen atom (SiH yl) of silicon atom bonding, SiH in molecule base and aforementioned (A) composition, (B) composition and (D) thiazolinyl with silicon atom bonding in the composition undertaken crosslinkedly by the hydrosilylation addition reaction, as being used for the solidifying agent that composition solidifies is worked.Should (E) composition organic hydrogen polysiloxanes represent with following average composition formula IV, preferably use have at least 2 in 1 molecule, preferred more than 3, more preferably 3～100, the organic hydrogen polysiloxanes of the hydrogen atom (SiH yl) of further preferred 3～50 silicon atom bondings.
R
3 cHdSiO
(4-c-d)/2 …(Ⅳ)
(in the formula, R
3For the carbonatoms that is same to each other or different to each other is 1～10, preferred 1～8 not replacement or the monovalence alkyl that replaces.In addition, c is that 0.7～2.1, d is 0.001～1.0, and c+d is satisfied 0.8～3.0 positive number.)
At this, as R
3The monovalence alkyl, can enumerate and R
1In the same alkyl of illustrative alkyl, preferably do not have the alkyl of unsaturated group of aliphatic series.In addition, c is preferably 0.8～2.0, d and is preferably 0.01～1.0, c+d and is preferably 1.0～2.5, and the molecular structure of organic hydrogen polysiloxanes can be straight chain shape, ring-type, a chain, three-dimensional netted any structure.At this moment, preferably using the number (or polymerization degree) of the Siliciumatom in 1 molecule to be 2～300, being in particular under the room temperature (25 ℃) about 4～150 is liquid organic hydrogen polysiloxanes.Need to prove, can be positioned at midway any of molecule chain end, molecular chain with the hydrogen atom of silicon atom bonding, also can be positioned at both.
Organic hydrogen polysiloxanes as above-mentioned (E) composition, can enumerate: 1,1,3, the 3-tetramethyl disiloxane, 1,3,5,7-tetramethyl-ring tetrasiloxane, three (hydrogen dimethylamino base siloxy-) methyl-monosilane, three (hydrogen dimethylamino base siloxy-) phenyl silane, the methyl hydrogen cyclopolysiloxane, methyl hydrogen siloxane dimethyl siloxane cyclocopolymer, the methylhydrogenpolysi,oxane of two terminal trimethylsiloxy end-blockings, the dimethylsiloxane methylhydrogensiloxacopolymer copolymer of two terminal trimethylsiloxy end-blockings, the dimethyl polysiloxane of two terminal dimethyl hydrogen siloxy-end-blockings, the dimethylsiloxane methylhydrogensiloxacopolymer copolymer of two terminal dimethyl hydrogen siloxy-end-blockings, the methyl hydrogen siloxane diphenyl siloxane multipolymer of two terminal trimethylsiloxy end-blockings, the methyl hydrogen siloxane diphenyl siloxane dimethylsiloxane copolymer of two terminal trimethylsiloxy end-blockings, the methyl hydrogen siloxane methylphenyl siloxane dimethylsiloxane copolymer of two terminal trimethylsiloxy end-blockings, the methyl hydrogen siloxane dimethyl siloxane diphenyl siloxane multipolymer of two terminal dimethyl hydrogen siloxy-end-blockings, the methyl hydrogen siloxane dimethyl siloxane methylphenyl siloxane multipolymer of two terminal dimethyl hydrogen siloxy-end-blockings, by (CH
3) 2HSiO
1/2Unit and (CH
3) 3SiO
1/2Unit and SiO
4/2The multipolymer of cell formation, by (CH
3) 2HSiO
1/2Unit and SiO
4/2The multipolymer of cell formation, by (CH
3) 2HSiO
1/2Unit and SiO
4/2Unit and (C
6H5) SiO
3/2The part or all of material that replaced with other alkyl or phenyl etc. of methyl etc. in the multipolymer of cell formation or these exemplary compounds.
The use level of organic hydrogen polysiloxanes is 0.2～20 mass parts with respect to total 100 mass parts of (A)～(D) composition, be preferably 0.3～10 mass parts, above-mentioned organopolysiloxane and hydrogen atom silicon atom bonding (SiH yl) and (A) composition, (B) composition and (D) mol ratio (SiH base/thiazolinyl) of the total amount of in the composition and thiazolinyl silicon atom bonding be preferred 0.8～10.0,1.0～5.0 amount particularly preferably.This ratio is less than 0.8 o'clock, sometimes crosslinkedly becomes insufficient, becomes the rubber that is clamminess, when its greater than 10.0 the time, might in forming composition, see foaming, or from the demoulding difficult of mould.
Aerosil as (F) composition is essential for silicon rubber being given sufficient intensity.Aerosil is 150m according to the specific surface area of BET method
2More than/the g, be generally 150～400m
2/ g is preferably 150～350m
2/ g, when its less than 150m
2During/g, not only can not obtain sufficient intensity, and the transparency of forming composition reduces also, when its greater than 400m
2During/g, might cooperate difficult, or variable color occurs.
These aerosils can directly use, but using when having carried out in advance aerosil that hydrophobization processes or preparation composition with surface treatment agent, preferably by with silicone oil (i.e. (A) composition organopolysiloxane) mixing the time, adding surface treatment agent, in the presence of a small amount of water, mixing, in composition, carry out the hydrophobization processing as required and use.As this surface treatment agent, can use alkylalkoxy silane, alkyl chlorosilane, alkyl silazane, silane coupling agent, titanic acid ester is known any a kind of materials such as treatment agent, fatty acid ester, in addition, can simultaneously or use more than 2 kinds in the different time.
The use level of aerosil is 10～50 mass parts with respect to total 100 mass parts of (A)～(D) composition, is preferably 10～45 mass parts, is particularly preferably 15～40 mass parts.Use level can not obtain sufficient rubbery intensity during less than 10 mass parts, in addition, when its during greater than 50 mass parts, hardness raises.
As the addition reaction catalyst of (G) composition, can enumerate: platinum group catalyst, palladium series catalyst, the rhodium series catalysts etc. such as the complex compound of reactant, Platinic chloride and the olefines of platinum black, platinum chloride (IV), Platinic chloride, Platinic chloride and monohydroxy-alcohol, two (etheric acid) platinum.
Need to prove, the use level of this addition reaction catalyst can be set as catalytic amount, usually, as the platinum metals, reach (E) the total quality of composition with respect to (A), (B), (D), be 0.5～1,000ppm is in particular about 1～500ppm.
In addition curing rubber composition of the present invention (rubber product forming composition for baby), as other composition, cooperate as required precipitated silica, silica powder, diatomite, the weighting agent of calcium carbonate and so on, or carbon black, electroconductive zinc oxide, the conductive agents such as metal powder, nitrogenous compound or acetylenic compound, phosphorus compound, the nitrile based compound, carboxylicesters, tin compound, mercury compound, the hydrosilylation reactions control agents such as sulphur compound, ferric oxide, the heat-resistant agent of cerium oxide and so on, the internal mold releases such as dimethicone oils, the binding property imparting agent, thixotropy imparting agents etc. are for arbitrarily.
Molding composition of the present invention can be by mixing above-mentioned each composition to make, the composition of gained preferably is liquid material room temperature (25 ℃) is lower, and particularly preferably the viscosity 25 ℃ the time is 50～5,000Pas, particularly preferably 100～3,000Pas.Need to prove, in the present invention, viscosity can utilize rotational viscosimeter to measure.
Moulding, curing as this molding composition can adopt ordinary method, as the method for forming, preferably adopt liquid injection moulding.In addition, as condition of cure, can adopt 120～230 ℃ lower 3 seconds～10 minutes, preferably 150～210 ℃ of lower heat treated conditions of about 5 seconds～3 minutes.
With regard to molding composition of the present invention, be cured and the hardness that records according to sclerometer A sclerometer of the cured article (silicon rubber) that obtains is 10～30, be in particular 12～28.Above-mentioned hardness is crossed when hanging down, and can not obtain sufficient rubbery intensity (tensile strength, tear strength), when it is too high, as rubber items for baby such as lactation sucker for drinking purposes or Pacifiers for baby the time, obstacle occurs in the interlock characteristic.
In addition, with regard to the silicon rubber of gained, preferred tensile strength is more than the 3.0MPa, more preferably more than the 3.5MPa, particularly preferably more than the 4MPa, tear strength [meniscus, CrescentType] is more than the 10kN/m, more preferably more than the 12kN/m, be particularly preferably more than the 15kN/m, elongation at break is preferably more than 400%, more preferably more than 450%, is particularly preferably more than 500%.At this, tensile strength, tear strength, elongation at break can utilize the method take JIS-K6249 as foundation to measure.
This silicon rubber is suitable for the babies such as lactation sucker for drinking purposes or Pacifier for baby and suckes the rubber item for baby of stinging or sucking in mouth.
[embodiment]
Below, utilize embodiment and comparative example to specifically describe this invention, but the present invention is not limited to following embodiment.Need to prove, in following example, part expression mass parts.In addition, mean polymerisation degree represents weight average degree of polymerization.
[embodiment 1]
Be that 750 (1) 60 part of dimethyl polysiloxane, specific surface area are 300m with two terminal mean polymerisation degree with the dimethylvinylsiloxy end-blocking
2After 2.0 parts of 40 parts of the aerosils of/g (Japanese ア エ ロ ジ Le society system, ア エ ロ ジ Le 300), 8 parts of hexamethyldisilazanes, water at room temperature mix 30 minutes, be warming up to 150 ℃, continue to stir 3 hours and cooled off, obtain the silicon rubber matrix.In 100 parts of this silicon rubber matrixes, add (1) 20 part of above-mentioned dimethyl polysiloxane, two terminal mean polymerisation degree with the trimethylsiloxy end-blocking and be 8,000 10 parts of dimethyl polysiloxane rubbers, by (CH
3) 3SiO
1/2Unit and CH
2=CH (CH
3) 2SiO
1/2Unit and SiO
2Resinous material multipolymer (the 2) [[(CH of cell formation
3) 3SiO
1/2Unit+CH
2=CH (CH
3) 2SiO
1/2The unit]/SiO
2Unit=0.90, contents of ethylene=0.0008mol/g, weight-average molecular weight 2,200] 5 parts, continue to stir after 30 minutes, further add two terminal mean polymerisation degree with the trimethylsiloxy end-blocking and be 20 parts of 70 dimethyl polysiloxanes, has methylhydrogenpolysi,oxane (the 3) (polymerization degree 17 of SiH base as linking agent at two ends and side chain, SiH base unit weight 0.0032mol/g) 3.9 parts [thiazolinyl in the SiH base/dimethyl polysiloxane (1) in the methylhydrogenpolysi,oxane (3) and the total of resinous material multipolymer (2)=1.8 (moles/mole)], as 0.05 part of the ethynylcyclohexanol that reacts control agent, continue to stir 15 minutes, obtain rubber composition [the BS type viscometer under 25 ℃, No. 7 rotors, measurement result under the 10rpm is 800Pas].
To after in this rubber composition, mixing 0.1 part of platinum catalyst (Pt concentration 1 quality %), carrying out 120 ℃/10 minutes cure under pressures, in baking oven, carry out the cured article of 150 ℃/1 hour after fixing, based on JIS-K6249, the result that hardness, tensile strength, elongation at break, tear strength (crescent) are measured and utilization refer to that the result of determination of the rubber surface that touches is illustrated in the table 1.
[embodiment 2]
Be that the specific surface area according to the BET method that 750 (1) 70 part of dimethyl polysiloxane, effects on surface have carried out the hydrophobization processing is 230m with two terminal mean polymerisation degree with the dimethylvinylsiloxy end-blocking
2After 1.0 parts of 30 parts of the aerosils of/g (ト Network ヤ マ society system, レ オ ロ シ one Le DS-30S), 2 parts of hexamethyldisilazanes, water at room temperature mix 30 minutes, be warming up to 150 ℃, continue to stir 3 hours and cooled off, obtain the silicon rubber matrix.In 100 parts of this silicon rubber matrixes, add two terminal mean polymerisation degree with the dimethylvinylsiloxy end-blocking and be 500 (4) 20 parts of dimethyl polysiloxanes, two ends with the mean polymerisation degree of dimethylvinylsiloxy end-blocking be 8,000 (5) 10 parts of dimethyl polysiloxane rubbers, by (CH
3) 3SiO
1/2Unit and CH
2=CH (CH
3) 2SiO
1/2Unit and SiO
2Resinous material multipolymer (the 6) [[(CH of cell formation
3) 3SiO
1/2Unit+CH
2=CH (CH
3) 2SiO
1/2The unit]/SiO
2Unit=1.2, contents of ethylene=0.0005mol/g, weight-average molecular weight 1,500] 8 parts, continue to stir after 30 minutes, further add two terminal mean polymerisation degree with the trimethylsiloxy end-blocking and be 20 parts of 90 dimethyl polysiloxanes, has methylhydrogenpolysi,oxane (the 3) (polymerization degree 17 of SiH base as linking agent at two ends and side chain, SiH base unit weight 0.0032mol/g) the 5.4 parts [SiH base/dimethyl polysiloxanes (1) in the methylhydrogenpolysi,oxane (3), dimethyl polysiloxane (4), thiazolinyl in the total of dimethyl polysiloxane rubber (5) and resinous material multipolymer (6)=2.3 (moles/mole)], as 0.05 part of the ethynylcyclohexanol that reacts control agent, continue to stir 15 minutes, obtain rubber composition [the BS type viscometer under 25 ℃, No. 7 rotors, measurement result under the 10rpm is 600Pas].
Table 1 expression to after in this rubber composition, mixing 0.1 part of platinum catalyst (Pt concentration 1 quality %), carrying out 120 ℃/10 minutes cure under pressures, in baking oven, carry out the cured article of 150 ℃/1 hour after fixing, based on JIS-K6249, the result that hardness, tensile strength, elongation at break, tear strength (crescent) are measured and utilization refer to the result of determination of the rubber surface that touches.
[embodiment 3]
Be that 500 (4) 60 parts of dimethyl polysiloxanes, specific surface area are 300m with two terminal mean polymerisation degree with the dimethylvinylsiloxy end-blocking
2After 2.0 parts of 40 parts of the aerosils of/g (Japanese ア エ ロ ジ Le society system, ア エ ロ ジ Le 300), 8 parts of hexamethyldisilazanes, water at room temperature mix 30 minutes, be warming up to 150 ℃, continue to stir 3 hours and cooled off, obtain the silicon rubber matrix.In 100 parts of this silicon rubber matrixes, add two terminal mean polymerisation degree with the dimethylvinylsiloxy end-blocking and be 1,100 (7) 40 parts of dimethyl polysiloxanes, embodiment 1 by (CH
3) 3SiO
1/2Unit and CH
2=CH (CH
3) 2SiO
1/2Unit and SiO
2(2) 5 parts of the resinous material multipolymers of cell formation, continue to stir after 30 minutes, further add methylhydrogenpolysi,oxane (the 8) (polymerization degree 15 that only has the SiH base at two ends as linking agent, SiH base unit weight 0.0018mol/g) 1.4 part, with trimethylsiloxy end-blocking two ends, and methylhydrogenpolysi,oxane (the 9) (polymerization degree 82 that has the SiH base at side chain, SiH base unit weight 0.0051mol/g) the 1.9 parts [SiH base/dimethyl polysiloxanes (4) in the total of methylhydrogenpolysi,oxane (8) and (9), thiazolinyl in the total of dimethyl polysiloxane (7) and resinous material multipolymer (2)=1.5 (moles/mole)], as 0.05 part of the ethynylcyclohexanol that reacts control agent, continue to stir 15 minutes, obtain rubber composition [the BS type viscometer under 25 ℃, No. 7 rotors, measurement result under the 10rpm is 500Pas].
Table 1 expression to after in this rubber composition, mixing 0.1 part of platinum catalyst (Pt concentration 1 quality %), carrying out 120 ℃/10 minutes cure under pressures, in baking oven, carry out the cured article of 150 ℃/1 hour after fixing, based on JIS-K6249, the result that hardness, tensile strength, elongation at break, tear strength (crescent) are measured and utilization refer to the result of determination of the rubber surface that touches.
[comparative example 1]
Be that 750 (1) 60 part of dimethyl polysiloxane, specific surface area are 300m with two terminal mean polymerisation degree with the dimethylvinylsiloxy end-blocking
2After 2.0 parts of 40 parts of the aerosils of/g (Japanese ア エ ロ ジ Le society system, ア エ ロ ジ Le 300), 8 parts of hexamethyldisilazanes, water at room temperature mix 30 minutes, be warming up to 150 ℃, continue to stir 3 hours and cooled off, obtain the silicon rubber matrix.In 100 parts of this silicon rubber matrixes, add (1) 20 part of above-mentioned dimethyl polysiloxane, continue to stir after 30 minutes, further add two terminal mean polymerisation degree with the trimethylsiloxy end-blocking and be 20 parts of 70 dimethyl polysiloxanes, has methylhydrogenpolysi,oxane (the 3) (polymerization degree 17 of SiH base as linking agent at two ends and side chain, SiH base unit weight 0.0032mol/g) 1.6 parts [thiazolinyl in the SiH base/dimethyl polysiloxane (1) in the methylhydrogenpolysi,oxane (3)=1.8 (moles/mole)], as 0.05 part of the ethynylcyclohexanol that reacts control agent, continue to stir 15 minutes, obtain rubber composition [the BS type viscometer under 25 ℃, No. 7 rotors, measurement result under the 10rpm is 300Pas].
Table 1 expression to after in this rubber composition, mixing 0.1 part of platinum catalyst (Pt concentration 1 quality %), carrying out 120 ℃/10 minutes cure under pressures, in baking oven, carry out the cured article of 150 ℃/1 hour rear elongation at break, based on JIS-K6249, the result that hardness, tensile strength, elongation at break, tear strength (crescent) are measured and utilization refer to the result of determination of the rubber surface that touches.
[comparative example 2]
Be that the specific surface area according to the BET method that 750 (1) 70 part of dimethyl polysiloxane, effects on surface have carried out the hydrophobization processing is 230m with two terminal mean polymerisation degree with the dimethylvinylsiloxy end-blocking
2After 1.0 parts of 30 parts of the aerosils of/g (Tokuyama society system, レ オ ロ シ one Le DS-30S), 2 parts of hexamethyldisilazanes, water at room temperature mix 30 minutes, be warming up to 150 ℃, continue to stir 3 hours and cooled off, obtain the silicon rubber matrix.In 100 parts of this silicon rubber matrixes, add two terminal mean polymerisation degree with the dimethylvinylsiloxy end-blocking and be (4) 20 parts of 500 dimethyl polysiloxanes, two terminal mean polymerisation degree with the dimethylvinylsiloxy end-blocking are 8, (5) 10 parts of 000 dimethyl polysiloxane rubbers, continue to stir after 30 minutes, further add and have methylhydrogenpolysi,oxane (the 3) (polymerization degree 17 of SiH base as linking agent at two ends and side chain, SiH base unit weight 0.0032mol/g) the 2.5 parts [SiH base/dimethyl polysiloxanes (1) in the methylhydrogenpolysi,oxane (3), thiazolinyl in the total of dimethyl polysiloxane (4) and dimethyl polysiloxane rubber (5)=2.3(moles/mole)], as 0.05 part of the ethynylcyclohexanol that reacts control agent, continue to stir 15 minutes, obtain rubber composition [the BS type viscometer under 25 ℃, No. 7 rotors, measurement result under the 10rpm is 900Pas].
Table 1 expression to after in this rubber composition, mixing 0.1 part of platinum catalyst (Pt concentration 1 quality %), carrying out 120 ℃/10 minutes cure under pressures, in baking oven, carry out the cured article of 150 ℃/1 hour after fixing, based on JIS-K6249, the result that hardness, tensile strength, elongation at break, tear strength (crescent) are measured and utilization refer to the result of determination of the rubber surface that touches.
[comparative example 3]
Be that 500 (4) 60 parts of dimethyl polysiloxanes, specific surface area are 300m with two terminal mean polymerisation degree with the dimethylvinylsiloxy end-blocking
2After 2.0 parts of 40 parts of the aerosils of/g (Japanese ア エ ロ ジ Le society system, ア エ ロ ジ Le 300), 8 parts of hexamethyldisilazanes, water at room temperature mix 30 minutes, be warming up to 150 ℃, continue to stir 3 hours and cooled off, obtain the silicon rubber matrix.Adding two terminal mean polymerisation degree with the dimethylvinylsiloxy end-blocking in 100 parts of this silicon rubber matrixes is 1, (7) 40 parts of 100 dimethyl polysiloxanes, continue to stir after 30 minutes, further add methylhydrogenpolysi,oxane (the 8) (polymerization degree 15 that only has the SiH base at two ends as additive, SiH base unit weight 0.0018mol/g) 0.7 part, the two terminal trimethylsiloxy end-blockings of using, and methylhydrogenpolysi,oxane (the 9) (polymerization degree 82 that has the SiH base at side chain, SiH base unit weight 0.0051mol/g) 1.0 parts [thiazolinyl in the SiH base/dimethyl polysiloxane (4) in the total of methylhydrogenpolysi,oxane (8) and (9) and the total of dimethyl polysiloxane (7)=1.5] (moles/mole)], as 0.05 part of the ethynylcyclohexanol that reacts control agent, continue to stir 15 minutes, obtain rubber composition [the BS type viscometer under 25 ℃, No. 7 rotors, measurement result under the 10rpm is 400Pas].
Table 1 expression to after in this rubber composition, mixing 0.1 part of platinum catalyst (Pt concentration 1 quality %), carrying out 120 ℃/10 minutes cure under pressures, in baking oven, carry out the cured article of 150 ℃/1 hour after fixing, based on JIS-K6249, the result that hardness, tensile strength, elongation at break, tear strength (crescent) are measured and utilization refer to the result of determination of the rubber surface that touches.
[table 1]
Claims (16)
1. rubber item for baby, it is used for the baby suckes in mouth and stings or suck, and is characterised in that, and the hardness of utilizing sclerometer A sclerometer to record is 10～30, and it comprises the cured article of addition curing rubber composition, and described addition curing rubber composition contains:
(A) containing at least 2 thiazolinyl, mean polymerisation degree with silicon atom bonding in 1 molecule is below 1,500, at room temperature is the organopolysiloxane of liquid: 100 mass parts,
(B) containing 0～5 thiazolinyl, mean polymerisation degree with silicon atom bonding in 1 molecule is the gluey organopolysiloxane of making a living under the room temperature more than 2,000: 0～50 mass parts,
(C) do not have addition reactivity functional group, mean polymerisation degree is the organopolysiloxane below 300: 0～50 mass parts,
(D) with R
3SiO
1/2Unit and SiO
2The unit is main component, R
3SiO
1/2Unit and SiO
2Mol ratio [the R of unit
3SiO
1/2/ SiO
2] be 0.5～1.5 and contain 5 * 10
-3～1 * 10
-4The resinous material multipolymer of the vinyl of mol/g: 0.1～20 mass parts, in the formula, R is the monovalence alkyl that does not replace or replace,
(E) contain at least 2 organic hydrogen polysiloxanes with the hydrogen atom of silicon atom bonding in 1 molecule: total 100 mass parts with respect to (A)～(D) composition are 0.2～20 mass parts,
(F) specific surface area according to the BET method is 150m
2The aerosil that/g is above: total 100 mass parts with respect to (A)～(D) composition are 10～50 mass parts,
(G) addition reaction catalyst: catalytic amount.
2. rubber item for baby as claimed in claim 1, wherein, (B) use level of composition is 5～50 mass parts with respect to 100 mass parts (A) composition.
3. rubber item for baby as claimed in claim 1, wherein, (C) use level of composition is 5～50 mass parts with respect to 100 mass parts (A) composition.
4. rubber item for baby as claimed in claim 1, wherein, the viscosity under 25 ℃ is the scope of 50～5,000Pas, is used for liquid injection molding.
5. rubber item for baby as claimed in claim 1, tensile strength is more than the 3.0MPa, elongation at break is more than 400%.
6. rubber item for baby as claimed in claim 1, tear strength is more than the 10kN/m.
7. such as each described rubber item for baby in the claim 1～6, it is the lactation sucker for drinking purposes.
8. such as each described rubber item for baby in the claim 1～6, it is Pacifier for baby.
9. rubber product forming composition for baby, it is the molding composition of sucking the rubber item for baby of stinging or sucking for the baby in mouth, be characterised in that, it comprises the addition reaction curable silicone rubber composition, it is 10～30 cured article that described addition reaction curable silicone rubber composition is given according to the scleroscopic hardness of sclerometer A by curing, and contains:
(A) containing at least 2 thiazolinyl, mean polymerisation degree with silicon atom bonding in 1 molecule is below 1,500, at room temperature is the organopolysiloxane of liquid: 100 mass parts,
(B) containing 0～5 thiazolinyl, mean polymerisation degree with silicon atom bonding in 1 molecule is the gluey organopolysiloxane of making a living under the room temperature more than 2,000: 0～50 mass parts,
(C) do not have addition reactivity functional group, mean polymerisation degree is the organopolysiloxane below 300: 0～50 mass parts,
(D) with R
3SiO
1/2Unit and SiO
2The unit is main component, R
3SiO
1/2Unit and SiO
2Mol ratio [the R of unit
3SiO
1/2/ SiO
2] be 0.5～1.5 and contain 5 * 10
-3～1 * 10
-4The resinous material multipolymer of the vinyl of mol/g: 0.1～20 mass parts, in the formula, R is the monovalence alkyl that does not replace or replace,
(E) contain at least 2 organic hydrogen polysiloxanes with the hydrogen atom of silicon atom bonding in 1 molecule: total 100 mass parts with respect to (A)～(D) composition are 0.2～20 mass parts,
(F) specific surface area according to the BET method is 150m
2The aerosil that/g is above: total 100 mass parts with respect to (A)～(D) composition are 10～50 mass parts,
(G) addition reaction catalyst: catalytic amount.
10. molding composition as claimed in claim 9, wherein, (B) use level of composition is 5～50 mass parts with respect to 100 mass parts (A) composition.
11. molding composition as claimed in claim 9, wherein, (C) use level of composition is 5～50 mass parts with respect to 100 mass parts (A) composition.
12. molding composition as claimed in claim 9, wherein, the viscosity under 25 ℃ is the scope of 50～5,000Pas, is used for liquid injection molding.
13. molding composition as claimed in claim 9, the tensile strength of cured article are more than the 3.0MPa, elongation at break is more than 400%.
14. molding composition as claimed in claim 9, wherein, the tear strength of cured article is more than the 10kN/m.
15. such as each described molding composition in the claim 9～14, wherein, rubber item for baby is the lactation sucker for drinking purposes.
16. such as each described molding composition in the claim 9～14, wherein, rubber item for baby is Pacifier for baby.
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| CN104109389A (en) * | 2014-06-19 | 2014-10-22 | 滁州天成有机硅高分子材料有限公司 | Silicone rubber compound for producing rubber nipples |
| CN104292571A (en) * | 2014-10-28 | 2015-01-21 | 宁波爱乐宝婴儿用品有限公司 | Infant pacifier containing konjac glucomannan composite gel and preparation method thereof |
| CN104825340A (en) * | 2015-05-06 | 2015-08-12 | 华逸母婴用品有限公司 | Infant food pharyngeal apparatus |
| CN107711577A (en) * | 2017-12-01 | 2018-02-23 | 新希望六和股份有限公司 | One broad sow lactation backing plate |
| CN109312160A (en) * | 2016-06-17 | 2019-02-05 | 信越化学工业株式会社 | Addition curing liquid silicon rubber composition |
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| CN103408946B (en) * | 2013-07-16 | 2015-04-29 | 福建农林大学 | Konjac glucomannan composite gel-containing baby nipple and preparation method thereof |
| CN110741048B (en) | 2017-06-15 | 2022-03-22 | 信越化学工业株式会社 | Silicone composition and method for preparing the same |
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| JP2019189723A (en) * | 2018-04-24 | 2019-10-31 | 信越化学工業株式会社 | High transparent addition curable liquid silicone rubber composition for led lamp, and led lamp |
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| JP3540356B2 (en) * | 1994-03-14 | 2004-07-07 | 東レ・ダウコーニング・シリコーン株式会社 | Conformal coating agent |
| JP3912525B2 (en) * | 2002-12-12 | 2007-05-09 | 信越化学工業株式会社 | Addition-curing silicone rubber composition and adhesive rubber sheet |
| JP2004323764A (en) * | 2003-04-28 | 2004-11-18 | Ge Toshiba Silicones Co Ltd | Adhesive polyorganosiloxane composition |
| JP4804775B2 (en) * | 2005-03-18 | 2011-11-02 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Curable polyorganosiloxane composition for seal and gasket |
| JP5179302B2 (en) * | 2008-09-11 | 2013-04-10 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Self-adhesive polyorganosiloxane composition |
| JP2011009346A (en) * | 2009-06-24 | 2011-01-13 | Shin-Etsu Chemical Co Ltd | Optical semiconductor device |
| JP5257297B2 (en) * | 2009-08-27 | 2013-08-07 | 信越化学工業株式会社 | Addition-curing silicone rubber composition |
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2011
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| CN104109389A (en) * | 2014-06-19 | 2014-10-22 | 滁州天成有机硅高分子材料有限公司 | Silicone rubber compound for producing rubber nipples |
| CN104292571A (en) * | 2014-10-28 | 2015-01-21 | 宁波爱乐宝婴儿用品有限公司 | Infant pacifier containing konjac glucomannan composite gel and preparation method thereof |
| CN104825340A (en) * | 2015-05-06 | 2015-08-12 | 华逸母婴用品有限公司 | Infant food pharyngeal apparatus |
| CN104825340B (en) * | 2015-05-06 | 2016-03-23 | 华逸母婴用品有限公司 | Infant food masticatory apparatus |
| CN109312160A (en) * | 2016-06-17 | 2019-02-05 | 信越化学工业株式会社 | Addition curing liquid silicon rubber composition |
| TWI706008B (en) * | 2016-06-17 | 2020-10-01 | 日商信越化學工業股份有限公司 | Addition hardening liquid silicone rubber composition |
| CN109312160B (en) * | 2016-06-17 | 2021-05-11 | 信越化学工业株式会社 | Addition-curable liquid silicone rubber composition |
| CN107711577A (en) * | 2017-12-01 | 2018-02-23 | 新希望六和股份有限公司 | One broad sow lactation backing plate |
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