JPS63256629A - Production of silicone-modified resin - Google Patents

Abstract

PURPOSE:To obtain a silicone-modified resin low in friction, excellent in water repellency, etc., and suitable for a paint, etc., without bleeding and a decrease in strength, by reacting a specified polyorganosiloxane having one modified terminal with an active hydrogen-containing resin. CONSTITUTION:A polyorganosiloxane having one modified terminal of formula I (wherein me is methyl, Pb is phenyl, R is methyl or phenyl, R<1> is H or methyl, m + n is 0-600, a and b are each 1-3, c is 1-300, and Q is a residue derived by removing one isocyanate group from a compound having a plurality of isocyanate groups) is prepared. The purpose silicone-modified resin is obtained by reacting this compound with an active hydrogen-containing resin (e.g., polyurethane or polyamide). Said compound of formula I can be obtained by reacting a compound of formula II with a compound having a plurality of isocyanate groups (e.g., tolylene diisocyanate).

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing a silicone-modified resin, and more specifically, the present invention relates to a method for producing a silicone-modified resin, and more specifically, a modified polydiorganosiloxane having an isocyanate group or a blocked isocyanate group at one end is processed into a polydiorganosiloxane containing active hydrogen. The present invention relates to a method for producing a silicone-modified resin with improved surface properties by reacting with a resin to form polyorganosiloxane side chains with inert terminals in the resin.

(Prior art) For the purpose of imparting water repellency, oil repellency, low friction properties, or antithrombotic properties to general-purpose resins, it has been conventionally practiced to modify polyol "Gafushiro-san". Conventional methods for imparting the above-mentioned properties of polyorganosiloxane to general-purpose resins include the simplest polymer blending method, which has functional groups such as silicon-bonded hydrogen groups, silanol groups, alcohol groups, or amino groups at both ends. A method of introducing a polyorganosiloxane chain into the main chain of a general-purpose resin by block copolymerization using polyorganosiloxane to form a block copolymer (for example, JP-A-60-238
315, JP-A No. 59-131629, etc.) and JP-A No. 58-189257, it is possible to combine thermoplastic general-purpose resins with polyorganosiloxanes by using polyorganosiloxanes that undergo addition reactions. Therefore, there is a method of forming a so-called interpenetrating network (IPN).

(Problems to be Solved by the Invention) However, in the polymer blending method, polyorganosiloxane has poor compatibility with general-purpose resins, so the polyorganosiloxane bleeds onto the surface of the mixture, so it can hardly be adopted.The above block copolymer In the method, the decrease in mechanical strength due to polyorganosiloxane chains increases as the proportion of polyorganosiloxane increases.In addition, in the method of forming IPNt, general-purpose resins and polyorganosiloxanes have poor compatibility. Therefore, it is not easy to form an evenly dispersed IPNt, and therefore a decrease in mechanical strength is likely to occur, and sufficient property improvement cannot be achieved unless polyorganocloxane is used in a fairly large proportion. cannot be obtained, and in this case, a bleed phenomenon occurs.

The purpose of the present invention is to solve the problems of the prior art, and to provide a general-purpose resin that has favorable properties such as low friction, water repellency, oil repellency, and antithrombotic properties, does not bleed, and has little strength loss. The purpose is to

(Means for Solving the Problems) The present invention is a method for producing a silicone-modified resin having a polyorganosiloxane chain whose end is capped with a trimethylsiloxy group as a side chain. Formula Me Ph (However, % Me is a methyl group, Ph is a phenyl group, R is a methyl group or a methyl group, % R1 is H or a methyl group,
m and n are each 0 or more, and the value of m+n is θ ~ 6
00, a is 1.2 or 3, b is 1.2 or 3,
C is 1-300. Q represents a residue obtained by removing one isocyanate group from a compound having at least two or more isocyanate groups, or a group in which the isocyanate group is blocked in the residue, respectively. It is characterized by reacting organosiloxane with an active hydrogen-containing resin.

Regarding the active hydrogen-containing resin used in the present invention, all resins produced by conventional methods can be used, and there are no restrictions.

That is, the active hydrogen-containing resin used in the present invention includes, for example, polyurethane, polyurethane flare, polyurea, polyamide, polyamideimide, melamine resin, phenol resin, cellulose resin, polyvinyl alcohol and its derivatives, vinyl acetate and ethylene, styrene, and acrylic. partially saponified copolymers containing vinyl acetate as a constituent unit, such as copolymers with acid esters, methacrylic esters, crotonic acid or maleic acid, and hydroxyethyl methacrylate or hydroxypropyl methacrylate; Excluding acrylic esters or methacrylic esters, among copolymers containing methacrylic esters containing hydroxyl groups as a constituent unit, such as copolymers with acrylic acid, methacrylic acid, styrene, crotonic acid, maleic acid, etc. Any resin may be used as long as it has at least one kind of active hydrogen, and the molecular structure is not limited by whether or not it is heat softenable, nor is it limited by molecular weight or manufacturing method.

Next, regarding the modified polyorganosiloxane having at least one isocyanate group or blocked isocyanate group at the end of one molecular chain used as a modifier in the present invention, It is clear from "Containing Modified Polyorganosiloxane and Method for Producing the Same" (Japanese Patent Application No. 309773/1982), and an outline thereof will be explained below.

The compound has the general formula )-(0(CHXCHt)b)e-OH(E)(
However, the symbols and symbols used here have the same meanings as above. It can be obtained by completely reacting the one-end modified polyorganosiloxane represented by ) with a compound having at least two isocyanate groups or blocked isocyanate groups.

In order to protect the isocyanate groups of the isocyanate group-containing modified polyorganosiloxane obtained by reacting with a metal compound having at least two isocyanate groups, this may be blocked.

Compounds having at least two isocyanate groups include compounds commonly called diisocyanates, such as tolylene diisocyanate, 'diphenylmethane diisocyanate, dianisidine diisocyanate, diphenyl ether diisocyanate, bitolylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone. Diisocyanate, lysine diisocyanate methyl ester, metaxylene diisocyanate, 2.2゜4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isopropylidene bis(4-cyclohexyl isocyanate), cyclohexylmethane diisocyanate dimer, etc., and triphenylmethane. Compounds containing three or more isocyanate groups, such as triisocyanate, triisocyanate phenylthiophosphate, biuret or cyanurate forms of the above diisocyanates, and adducts of the above diisocyanates and polyhydric alcohols such as trimethylolpropane and trimethylolethane. In addition, prepolymers of these isocyanate group-containing compounds and polyhydric alcohols or compounds having two or more amine groups, which contain two or more isocyanate residues, etc. Almost any compound having an isocyanate group can be used. It is also possible to use so-called blocked isocyanates in which these isocyanate-based lower alcohols, lower monocarboxylic acids, phenols, oximes, lactams, or sodium bisulfate are blocked.

Further, the modified polyorganosiloxane of general formula 03) has the general formula (O (MesSiO(Me25iO)yl -(RPhSi
O)n)a-St-HMe(8-a) (However, the symbols and symbols used here have the same meanings as above.) The general formula 〇CHt-CHCHt- (0(CHR”) (CHt
) b ) e -OS iMesO) (However, symbols and symbols used here have the same meanings as above.) General formula (g) synthesized by addition reaction (hydrosilylation reaction) to a compound represented by Me(It-4) (MesSiO(MetSiO)rn-(RPhSiO
)n)a-8i --CsHa-(0(CHR"XC
H:) b) c-O8iMes (1 (However, symbols and symbols used here have the same meanings as above)) Obtained by treating the compound with a lower alcohol or an aqueous hydrochloric acid solution to remove the trimethylsilyl group be able to.

The H-modified polydiorganosiloxane with the general formula (0) has the general formula MesSiO(MetSIO)m-(RPhSiO)n
-M (F5 (where M indicates Na or Li. Other symbols and symbols have the same meanings as above.)
The living polymer on the left has silicon-bonded hydrogen represented by the general formula 〇) C1h-8t-HD) Me(a-a) (However, the symbols and symbols used here have the same meanings as above.) It can be obtained by reacting with a chlorosilane compound. In addition, compound (2) is obtained by converting the OH group of an unsaturated bond-containing compound represented by the general formula % (however, the symbols and symbols used here have the same meanings as above) into hexamethyldisilazane, etc. It can be obtained by silylation using a silylating agent.

Each of the above reaction steps can be carried out using well-known procedures and conditions, and does not require any special procedures.

Of course, in some cases, the compound of general 2〇 and the general formula (
It is also possible to first perform the hydrosilylation reaction with the chlorosilane compound in 2), and then react the reaction product with the general formula (trans)gluing polymer to synthesize the compound of the general formula (2).

Next, a method for silicone-modifying an active hydrogen-containing resin using the modifier obtained in this way will be explained.

Basically, by reacting a single-end modified polyorganosiloxane represented by the general formula (A) with an active hydrogen-containing resin, a polyorganosiloxane chain whose terminal end is blocked with a trimethylsiloxane group is introduced into a side chain. A new type of silicone modified resin is obtained. When carrying out the silicone modification reaction, the active hydrogen-containing resin can be dissolved in a solvent and reacted in a homogeneous solution state, or the active hydrogen-containing resin powder and the modifier can be mixed in the presence or absence of a solvent. The reaction can also be carried out in a solid-liquid mixed state. As a simpler method, the reaction can be carried out using extrusion, which is economically advantageous.

When the reaction is carried out in a homogeneous solution state, the solvent dissolves the active hydrogen-containing resin and is used as a modifying agent.
The most suitable one is one that can also dissolve the one-end modified polyorganosiloxane represented by A) and is inert to isocyanate groups. Examples of solvents vary depending on the three types of resin used, but for example, in the case of urethane, aromatic halides such as monochlorobenzene and dichlorobenzene, esters such as methyl isobutyl acetate and methoxybutyl acetate, methyl isobutyl ketone, and methyl ethyl ketone. , ketones such as fuchlorohexanone, ethers such as butyl ether, dioxane, anisole, methoxytoluene, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc. For polyamides, pyridine, N-methylpyrrolidone, N,N-dimethylacetamide, etc. Examples include amide solvents. These solvents may be newly added to K for modifying general-purpose resins, but it is preferable to distill off the solvent used when preparing the single-end modified polyorganosiloxane represented by the general formula (A) of the modifier. It may be used as is.

In any case, in the presence of such a solvent, the general-purpose resin and the one-end modified polyorganosiloxane represented by the general formula (2) are mixed and dissolved, and the mixture is heated to a temperature of 50° C. or higher to react.

The silicone modified resin solution thus obtained can be made into a silicone modified resin by adding a poor solvent to precipitate the resin.

Furthermore, when reacting the active hydrogen-containing resin powder and the modifier in a solid-liquid mixed state in the presence or absence of a solvent, the manner of reaction differs depending on the amount of solvent used. That is, when using a large amount of a solvent that does not have or has poor dissolving power for general-purpose resins, it is sufficient to use an ordinary stirring tank to heat the solvent to a temperature of 50"C or higher and cause the reaction to occur while stirring. This is a method that can be adopted when a large amount of solvent that has no or poor dissolving power for general-purpose resins is used when preparing the polyorganosiloxane of formula (4), and the solvent is distilled off from the polyorganosiloxane solution. The process can be omitted.

In addition, when using a small amount of solvent regardless of its solubility in general-purpose resin, or when using no solvent at all, a type of mixing that can stir the powder in a wet state is used instead of a normal stirring tank for liquids. The reaction is carried out using a machine at a temperature of 50°C or higher. Mixers that can be used in this method include, for example, ribbon mixers, screw mixers, rod mixers, multi-shaft paddle mixers, high-speed fluid mixers, Muller mixers, and the like. When a large amount of solvent is used, the solvent is separated by filtration and then dried, or most of the solvent is separated and the remaining solvent is distilled off while extrusion and granulation is carried out. If a small amount of solvent is used, either drying is carried out in the same manner or extrusion is carried out while distilling off the solvent. If no solvent is used at all, there is no need for a drying step as a post-process, but even in cases where a small amount of solvent is used, it is assumed that the reaction is not completed and unreacted modifier remains attached. In such cases, it may be better to wash the resin in a solvent that does not dissolve the general-purpose resin but only dissolves the modifier, and then separate and dry it. However, in general, if it is thought that the reaction is insufficient after reacting in a mixer, granulation using an extruder as a post-process is a simpler and more complete method to carry out the reaction. Economical.

Therefore, as is clear from the above, as a simpler reaction method, the third method is to react only in the extruder and granulate it as it is.
This method can also be adopted, and in the reaction of the present invention, a modified resin that can be used for practical purposes can also be produced using this method.

In addition, when reacting the active hydrogen-containing resin with the modifier, an acid catalyst such as an inorganic acid, an ester of phosphoric acid or phosphoric acid, or p-toluenesulfonic acid, N-methylmorpholine,
triethylamine, N,N-dimethylbenzylamine,
N*N'-dimethylpiperazine, triethylenediamine, N.

N, N', N'-tetramethylethylenediamine,
N, N, N', N'-tetramethylhexamethylenediamine, N, N, N', N'', N''-pentamethyldiethylenetriamine, hexamethylenetetramine, 1,8-diazabicyclo(5,4,0) -7-kundecene CD, B, U, etc.), or cobalt naphthenate, lead naphthenate, zinc naphthenate, stannous chloride, tin chloride, tri-n-butyltin acetate,
Trimethyltin hydroxide, dimethyltin dichloride, dibutyltin dilaurate, octylic acid
Tin, tetraoctyl titanate, cobalt octylate,
Metal catalysts such as antimony trichloride and the like can also be used and are preferred in terms of promoting the reaction.

[Effect]

As detailed above, the silicone-modified resin of the present invention can be produced by reacting with a modified polyorganosiloxane having at least one isocyanate group or a blocked isocyanate group at the end of a molecular chain. Structure 8 → where the polyorganosiloxane branches to the side chain of the resin tD, unlike the case where the polyorganosiloxane is introduced into the main chain of the active hydrogen-containing resin to form a block copolymer, the active hydrogen-containing resin originally It has become possible to impart properties such as low friction, water repellency, oil repellency, and antithrombotic properties based on polyorganosiloxane without reducing the mechanical strength of the polyorganosiloxane. Furthermore, in this case, the side chain-branched polyorganosiloxane has a trimethylsiloxy group at the other end and has no reactivity, so its movement is not restricted and it interacts with the active hydrogen-containing resin in the main chain. It is thought that this tends to move away from the main chain due to the poor compatibility of . When the silicone-modified resin of the present invention is used as it is or in active form, the polyorganosiloxane rises to the surface of the molded product, similar to the bleeding phenomenon that occurs when a simple polymer blend is used. However, in the case of the present invention, since the polyorganosiloxane is chemically bonded to the main chain, it is not liberated as polyorganosiloxane, and the sticky phenomenon does not occur.

Because of this effect, the silicone-modified resin of the present invention has low friction properties, that is, surface slipperiness, even if the amount of one-terminally modified polyorganosiloxane of general formula (2) used as a modifier is small. The result is a material fully endowed with the desirable properties of polyorganosiloxane. Therefore, a silicone-modified resin obtained by bonding a large amount of one-end modified polyorganosiloxane of the general formula (4) to a general-purpose resin can be simply blended with a general-purpose resin that is compatible with the modified resin. This makes it possible to express the effect as a denaturing agent.

〔Example〕

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples.

Example 1 (1) 4.4' for 1 mole of polyorganosiloxane, which is represented by the general formula % and has a molecular weight of about 1150 (n=12.2).
-Methylenebis(phenylisocyanate) (MDI)
1 mol was added and heated in dioxane solvent at 100°C for 2 hours. After death, the solvent was distilled off under reduced pressure.

(2) Pulverized commercially available general-purpose polyamide resin (Toray Kema Amiran (registered trademark) 1021) (base polymer) 9
0 parts (parts by weight, same hereinafter) of polyorganosiloxa 710 modified with isocyanate at one end obtained in (1)
1,8-diazabicyclo(5
゜4.0)-7-Undecene (D, B, U,) 0.01
The mixture was extruded into pellets at 230 to 240°C using an extruder.

(3) The pellets obtained in (2) were molded and the surface of the molded piece was checked for bleed by wiping the surface with a finger. As a result, no oil adhesion due to bleed was observed.

Table 1 shows the results of measuring tensile strength, tensile elongation at break, bending strength, bending modulus, and water contact angle.

Example 2 (1) 11 mol of MD was added to 1 mol of polyorganosiloxane, which is represented by the same general formula as used in Example 1 and has a molecular weight of about 4500 (n 57.4), and 100 mol of MD was added in dioxane solvent. After heating and reacting at °C for 2 hours, the solvent was distilled off under reduced pressure.

(2) The same commercially available polyamide resin used in Example 1 was pulverized, and 90 parts of the polyorganosiloxane compound modified with one terminal isocyanate obtained in (1) was added to 90 parts of the same.
0 parts of 1,8-diazabicyclo(
5,4゜0〕-7-undecene (D, B, U,
) Add 0.01 part and heat at 230-240°C in an extruder.
It was extruded into pellets.

(3) (2) Pellet) 1-The pellets were molded and the surface of the molded piece was checked for bleed by wiping the surface with a finger. As a result, no oil adhesion due to bleed was observed. Table 1 shows the results of measuring tensile strength, elongation, bending strength, bending modulus, and water contact angle.

Example 3 (1) 11 mol of MD was added to 1 mol of polyorganosiloxane, which is expressed by the same general formula as used in Example 1 and has a molecular weight of about 7100 (n=92.6), and the mixture was heated at 100°C in a dioxane solvent. After heating and reacting for 2 hours, the solvent was distilled off under reduced pressure.

(2) The same commercially available polyamide resin used in Example 1 was pulverized, and 90 parts of the polyorganosiloxane compound modified with one terminal isocyanate obtained in (1) was added to 90 parts of the same.
0 parts of 1,8-diazabicyclo(
5,4゜0〕-7-undecene (D, B, U, )
0.01 part was added thereto, and the mixture was extruded into pellets at 230 to 240°C using an extruder.

(3) The pellets of (2) were molded and the surface of the molded piece was checked for bleed by wiping with a finger. As a result, no oil adhesion due to bleed was observed.

Table 1 shows the results of measuring tensile strength, elongation, bending strength, bending modulus, and water contact angle.

Comparative Example 1 The same commercially available polyamide resin (base polymer) as in Example 1 was molded, and the molded piece was measured for tensile strength, elongation, bending strength, bending modulus, and water contact angle. The results are shown in Table IK.

Table 1 Notes (1) Tensile strength, elongation, bending strength and bending modulus:
(JIS K 6810 Hole J7 Mi) "Testing method for resin (nylon) molding materials".

(2) Measurement of contact angle: by Kyowa Contact Angle Meter (trademark) CA-P manufactured by Kyowa Kagaku ■.

Example 4 (1) 4.4′-
Methylenebis(phenylisocyanate)CMDI)1
After adding mol of methyl ethyl ketone and heating at 80° C. for 2 hours, the solvent was distilled off under reduced pressure.

(2) Pulverized commercially available general-purpose polyamide resin (Ube Industries ■
1 of polyorganosiloxane modified with isocyanate at one end obtained in (1) for 99 parts of P-1011FB)
1,8-diazabicyclo(5
,4,0)-7-undecene (D,B,U,)0.01
The mixture was extruded into pellets at 230 to 240°C using an extruder.

(3) The molded piece in (2) was molded, and the presence or absence of bleed was checked by wiping the surface of the molded piece with a finger. As a result, oil adhesion due to bleed was observed.

In addition, tensile strength, elongation, bending strength, bending modulus,
Table 2 shows the results of measuring the water contact angle, Izot impact strength (notched), and water absorption.

Comparative Example 2 Pellets of the same commercially available polyamide resin (pace polymer) as in Example 4 were molded, and the molded pieces were measured for tensile strength, elongation, bending strength, bending modulus, water contact angle, and isot impact strength (notched). ) and water absorption were measured.

The results are shown in Table 2.

Table 2 Notes (1) Tensile strength, elongation, bending strength and bending modulus:
(JIS K 6810 polyamide resin (nylon)
Molding material testing method].

(2) Measurement of contact angle: by Kyowa Contact Angle Meter (trademark) CA-P manufactured by Kyowa Kagaku ■.

Example 5 (1) 4.4'-methylenebis (
After adding 1.1 mol of phenyl incyane-) (MDI) and reacting by heating at 80°C for 2 hours in a 1,4-dioxane solvent, the solvent was distilled off under reduced pressure.

(2) Dissolve 68 parts of commercially available general-purpose polyurethane (CND Kasei Berecene (registered trademark) 2363-80AE) in 500 parts of 1.4-dioxane by heating at 110°C for 2 hrs.
), 32 parts of the polyorganosiloxane prepared in (1) was added thereto, and 1,8-diazabicyclo(5°4.0)-7-+/decene(D,B,U,)0 was added as a catalyst.
．． 01 part was added and heated at 110°C for 2 hours.

This reaction solution was poured into water to precipitate a resin, and the precipitated resin was dried and press-molded.

As a result of checking the presence or absence of bleed by wiping the surface of the molded piece with a finger, no oil adhesion due to bleed was observed. fk The tensile strength, elongation, hardness (Rockwell), water contact angle and tape peel strength of the molded piece were measured, and the whole blood coagulation time (Lee-White test) was measured for the dried modified resin product. The results are shown in Table 3.

Example 6 (1) 6 parts of the same commercially available polyurethane (base polymer) powder used in Example 5 was mixed with 1 part of the resin obtained in Example 5 (2), and 200 ~2
It was extruded at 20°C to form a pellet.

<2) The pellet of (1) was molded and the surface of the molded piece was checked for the presence of bleed by wiping the surface with a finger. As a result, no oil adhesion due to bleed was observed.

The results of measuring the tensile strength, elongation, hardness (Rockwell), water contact angle, and tape peel strength of the molded piece, as well as the whole blood coagulation time (Lee-
Table 3 shows the results of the White test).

Example 7 (1) 1 part of the resin obtained in Example 5 (2) was mixed with 14 parts of the same commercially available polyurethane (base polymer) powder as used in Example 5, and 200 ~
It was extruded at 220°C to form a pellet.

(2) The pellet of (1) was molded and the surface of the molded piece was checked for bleed by wiping with a finger. As a result, no oil adhesion due to bleed was observed.

The results of measuring the tensile strength, elongation, hardness (Rockwell), water contact angle, and tape peel strength of the molded piece, as well as the whole blood coagulation time (Lee-
Table 3 shows the results of the White test).

Comparative Example 3 A pellet of the same commercially available polyurethane (base polymer) as used in Example 5 was molded, and the tensile strength, elongation, hardness (Rockwell), water contact angle, and tape peel strength were measured for the molded piece. The results are shown in Table 3, as well as the results of measuring the whole blood coagulation time (Lee-White test) for the above pellets.

Table 3 (Note) (1) Tensile strength, elongation, bending strength and bending modulus:
Measured according to (JIS K 6301 vulcanized rubber physical test method).

(2) Measurement of contact angle: by Kyowa Contact Angle Meter (trademark') CA-P manufactured by Kyowa Chemical ■.

(3) 180 degree tape release adhesive tape: Nitto Mini-31B used Peeling speed: 300 m/m1n (4) Whole blood coagulation time by Lee-White method (written by Izumihara Kanai, "Clinical Test Methods Summary JP, 357, Metal Publishing ■) (Effect of the invention) According to the present invention, it has become possible to produce a silicone-modified resin having a structure in which polyorganosiloxane is branched in the side chain.Moreover, the branched polyorganosiloxane chain is as described in the function section. The resin produced according to the present invention can be chemically bonded to the main chain of a general-purpose resin using a modified polyorganosiloxane having an isocyanate group or a blocked isocyanate group at one end, so that the resin produced according to the present invention can be used in a conventional blending method. There is no bleeding phenomenon as in the IPNt-forming method, and there is no significant decrease in mechanical strength as in the block polymerization method. It has excellent effects.

Since the silicone-modified resin of the present invention has the above-mentioned favorable properties, it can be used as a material for sliding parts that do not run out of oil, and as a material for molded products that require low friction properties, such as paints for release paper. It can be advantageously used as a component of paints that require water repellency or oil repellency, or as a molding material in the medical field that requires antithrombotic properties. Therefore, the work efficiency is improved by easily separating from the mold during molding.

In addition, the general formula (
It has the advantage of being able to employ a simple reaction method in which the one-terminally modified polyorganosiloxane represented by 2) is reacted in an extruder and pelletized.

that's all

Claims (10)

[Claims] (1) General formula (A), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (A) (However, Me is a methyl group, Ph is a phenyl group, R is a methyl group or Phenyl group, R^1 is H or methyl group, m
and n are each 0 or more, and the value of m+n is 0 to 60
a number that is 0, a is 1, 2 or 3, b is 1, 2 or 3
, c represents 1 to 300, and Q represents a residue obtained by removing one isocyanate group from a compound having at least two or more isocyanate groups, or a group in which the isocyanate group is blocked in the residue. ) A method for producing a silicone-modified resin, which comprises reacting a single-terminally modified polyorganosiloxane represented by the following formula with an active hydrogen-containing resin. (2) The value of m+n in general formula (A) is 10 to 120
The method for producing a silicone-modified resin according to claim (1), characterized in that a one-terminally modified polyorganosiloxane is used. (3) Production of a silicone-modified resin according to claim 1 or 2, which uses a single-end modified polyorganosiloxane in which a=1 in general formula (A). Method. (4) Claim (1) characterized in that the reaction between the one-end modified polyorganosiloxane represented by the general formula (A) and the active hydrogen-containing resin is carried out in a homogeneous solution state in the presence of a solvent. A method for producing a silicone-modified resin according to any one of items 1 to 3. (5) A patent claim characterized in that the reaction between the one-end modified polyorganosiloxane represented by the general formula (A) and the active hydrogen-containing resin is carried out in a solid-liquid mixed state in the presence or absence of a solvent. A method for producing a silicone modified resin according to any one of items (1) to (3). (6) Claim (1) characterized in that the reaction between the one-end modified polyorganosiloxane represented by the general formula (A) and the active hydrogen-containing resin is carried out in an extruder.
A method for producing a silicone-modified resin according to any one of items 1 to 3. (7) Claim No. 1, characterized in that the reaction between the one-end modified polyorganosiloxane represented by the general formula (A) and the active hydrogen-containing resin is carried out in the presence of a catalyst.
The method for producing a silicone-modified resin according to any one of items 1) to (6). (8) The reaction between the one-end modified polyorganosiloxane represented by the general formula (A) and the active hydrogen-containing resin is carried out at a temperature of 50 to
A method for producing a silicone-modified resin according to any one of claims (1) to (7), characterized in that the process is carried out at 300°C. (9) In Q of the single-end modified polyorganosiloxane represented by the general formula (A), the blocked isocyanate group is a lower alcohol having 1 to 4 carbon atoms, or a lower alcohol having 2 to 4 carbon atoms.
The method for producing a silicone-modified resin according to any one of claims (1) to (8), characterized in that the silicone-modified resin is blocked with a monocarboxylic acid or a phenol. (10) The active hydrogen-containing resin is a partial polymer of polyurethane, polyurethane urea, polyurea, polyamide, polyamideimide, melamine resin, phenol resin, cellulose resin, polyvinyl alcohol and its derivatives, and a copolymer whose constituent components are vinyl acetate. The silicone according to any one of claims (1) to (9), characterized in that it is at least one type of copolymer containing a compound and a hydroxyl group-containing methacrylic acid ester as a constituent component. Method for producing modified resin.