JP2015199887A - silicone composition, silicone emulsion composition and fiber treatment agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition having high curing property even under a low temperature condition, excellent in storage stability, capable of adding good flexibility to a fiber as a fiber treatment agent and having excellent washing durability.SOLUTION: There is provided a silicone composition containing: 70 to 98 pts.mass of organopolysiloxane having a group represented by the general formula (1) at a molecule terminal or a side chain, (1), where Ris a bivalent hydrocarbon group having 1 to 8 carbon atoms, a is an integer of 0 to 4, and Ris each independently a hydrogen atom, a monovalent hydrocarbon group or an acyl group having 1 to 10 carbon atoms and at least one of group represented by Ris a hydrogen; and 2 to 30 pts.mass of (B) block polyisocyanate having two or more isocyanate groups in a molecule where 50% or more of the isocyanate group is blocked by a thermally dissociable blocking agent.

Description

  The present invention relates to a curable silicone composition containing a blocked polyisocyanate. Specifically, the present invention relates to a silicone composition, a silicone emulsion composition, and a fiber treatment agent that are excellent in curability at low temperatures.

Conventionally, various organopolysiloxanes such as dimethylpolysiloxane, epoxy group-containing polysiloxane, aminoalkyl group-containing polysiloxane have been widely used as treatment agents for imparting flexibility and smoothness to various fibers or fiber products. Yes. Among them, aminoalkyl group-containing organopolysiloxanes that can impart particularly good flexibility to various fibers or fiber products are often used. In particular, a fiber treatment agent mainly composed of an organopolysiloxane having an aminoalkyl group such as —C ₃ H ₆ NH ₂ group, —C ₃ H ₆ NHCH ₂ CH ₂ NH ₂ group (Japanese Patent Publication No. 48-1480, JP 54-43614, JP 57-43673, JP 60-185879, JP 60-185880, JP 64-61576, etc.) Widely used for showing.

  In recent years, there has been an increasing demand for higher functionality for clothing, and in the fiber treatment field, functional agents such as deodorants, antibacterial agents, disperse pigments, and disperse dyes have been added to impart various functions to fibers. It is processed on the fiber using a resin binder. For example, in JP-A-7-279053, silk fibroin is prevented from falling off by using a fiber treatment agent in which silk fibroin is blended in a resin emulsion such as polyurethane resin, polyester resin, and acrylic resin, and adhesion to fibers. Improvements have been made. In Japanese Patent Application Laid-Open No. 7-41733, natural product powder and urea-aldehyde resin powder are coated with a synthetic resin binder such as urethane resin, acrylic resin, polyester resin, etc. A natural product powder-containing surface treatment agent that suppresses generation of unpleasant odor during construction has been proposed.

  In order to maintain the functions of the fiber treatment agent itself such as flexibility and water absorption, and the functions exerted by various chemicals such as deodorizing function and antibacterial function over a long period, Various treatment agents and functional agents need to continue to adhere. For this reason, high washing durability is calculated | required by the fiber treatment agent and the resin binder.

Japanese Patent Publication No. 48-1480 Japanese Examined Patent Publication No. 54-43614 Japanese Examined Patent Publication No. 57-43673 JP 60-185879 A JP 60-185880 A Japanese Patent Application Laid-Open No. 64-61576 Japanese Patent Laid-Open No. 7-279053 Japanese Unexamined Patent Publication No. 7-41733

  However, flexibility and washing durability required for fiber processing are contradictory properties, and when a fiber treatment agent or binder resin having high washing durability is used for fiber processing, flexibility tends to be lost. Moreover, when processing a binder on a fiber, the process at high temperature was also a subject. From the above, the present invention has high curability even under low temperature treatment conditions, excellent storage stability, can impart good flexibility to the fiber as a fiber treatment agent, and has excellent washing durability The object is to provide a composition having both.

  As a result of investigations to solve the above problems, the present inventors have found that a silicone composition containing 70 to 98 parts by mass of an organopolysiloxane containing an amino group and 2 to 30 parts by mass of a specific block polyisocyanate. It has been found that it exhibits excellent curability even at low temperatures and is excellent in storage stability. Moreover, it has been found that by using the composition as a fiber treating agent, good flexibility can be imparted to the fiber and higher washing durability is exhibited, and the present invention has been made.

（式中、Ｒ^xは炭素数１〜８の２価炭化水素基であり、ａは０〜４の整数であり、Ｒ^yは互いに独立に、水素原子、炭素数１〜１０の１価炭化水素基又はアシル基であり、Ｒ^yで示される基のうち、少なくとも１つは水素原子である。）
（Ｂ）１分子中に２個以上のイソシアネート基を有し、このイソシアネート基の５０％以上が熱解離性ブロック剤で封鎖されたブロックポリイソシアネート２〜３０質量部と
を含有するシリコーン組成物。
［２］．（Ａ）成分のオルガノポリシロキサンに含まれる１つ以上のＮＨ基と、（Ｂ）成分のイソシアネート基との反応物である［１］に記載のシリコーン組成物。
［３］．（Ｂ）成分が、脂肪族及び／又は脂環族ジイソシアネートモノマーからなるポリイソシアネート構造を有するブロックポリイソシアネートである［１］又は［２］記載のシリコーン組成物。
[４].（Ｂ）成分の熱解離性ブロック剤が、オキシム系化合物、ピラゾール系化合物及び活性エチレン系化合物からなる群から選ばれる化合物である、[１]〜[３]のいずれかに記載のシリコーン組成物。
[５].[１]〜[４]のいずれかに記載のシリコーン組成物を含むシリコーンエマルション組成物。
[６].[１]〜[４]のいずれかに記載のシリコーン組成物を含む繊維処理剤。 Accordingly, the present invention provides the following silicone composition, silicone emulsion composition and fiber treatment agent.
[1]. (A) 70 to 98 parts by mass of an organopolysiloxane having a group represented by the following general formula (1) at the molecular end or side chain;

(In the formula, R ^x is a divalent hydrocarbon group having 1 to 8 carbon atoms, a is an integer of 0 to 4, R ^y is independently a hydrogen atom, a monovalent carbon atom having 1 to 10 carbon atoms. (It is a hydrogen group or an acyl group, and at least one of the groups represented by R ^y is a hydrogen atom.)
(B) A silicone composition containing 2 to 30 parts by mass of a blocked polyisocyanate having 2 or more isocyanate groups in one molecule and 50% or more of the isocyanate groups blocked with a heat dissociable blocking agent.
[2]. The silicone composition according to [1], which is a reaction product of one or more NH groups contained in the organopolysiloxane of component (A) and an isocyanate group of component (B).
[3]. The silicone composition according to [1] or [2], wherein the component (B) is a block polyisocyanate having a polyisocyanate structure composed of an aliphatic and / or alicyclic diisocyanate monomer.
[4]. The thermal dissociable blocking agent as component (B) is a compound selected from the group consisting of oxime compounds, pyrazole compounds and active ethylene compounds, according to any one of [1] to [3]. Silicone composition.
[5] A silicone emulsion composition comprising the silicone composition according to any one of [1] to [4].
[6] A fiber treatment agent comprising the silicone composition according to any one of [1] to [4].

  The silicone composition of the present invention has excellent low-temperature curability and storage stability, and the fiber treatment agent using the silicone composition can impart good flexibility to the fiber and is excellent in washing durability. Yes.

Hereinafter, the present invention will be described in detail.
[Silicone composition]
The silicone composition of the present invention is a silicone composition containing (A) 70 to 98 parts by mass of the following (A) organopolysiloxane and (B) 2 to 30 parts by mass of block polyisocyanate.

（式中、Ｒ^xは炭素数１〜８の２価炭化水素基であり、ａは０〜４の整数であり、Ｒ^yは互いに独立に、水素原子、炭素数１〜１０の１価炭化水素基又はアシル基であり、Ｒ^yで示される基のうち、少なくとも１つは水素原子である。） (A) An organopolysiloxane having a group represented by the following general formula (1) at the molecular end or side chain, and can be used singly or in appropriate combination of two or more.

(In the formula, R ^x is a divalent hydrocarbon group having 1 to 8 carbon atoms, a is an integer of 0 to 4, R ^y is independently a hydrogen atom, a monovalent carbon atom having 1 to 10 carbon atoms. (It is a hydrogen group or an acyl group, and at least one of the groups represented by R ^y is a hydrogen atom.)

  The organopolysiloxane of the present invention may have any of a linear structure, a branched structure, and a cyclic structure, but is preferably a linear structure. In the organopolysiloxane, the group represented by the general formula (1) is bonded to the silicon atom of the polysiloxane skeleton and may be present at either the molecular terminal or the side chain. The group represented by the general formula (1) may be 1 or more, preferably 2 or more, and more preferably 2 to 10 groups.

In the general formula (1), R ^x is a divalent hydrocarbon group having 1 to 8 carbon atoms. As the divalent hydrocarbon group, an alkylene group such as a methylene group, an ethylene group, a propylene group, and a butylene group is preferable, and among them, a propylene group is preferable. a is an integer of 0 to 4, and 1 or 2 is preferable.

In the general formula (1), R ^y is each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or an acyl group, and at least one of the groups represented by R ^y is a hydrogen atom. Preferably, 33% by mass of the total number of groups represented by R ^y is a hydrogen atom, and more preferably 50% or more is a hydrogen atom. The upper limit is not particularly limited, but may be 100%.

［上記式（２）〜（４）中、Ｒ⁴は互いに独立に、下記一般式（１）

（式中、Ｒ^xは炭素数１〜８の２価炭化水素基であり、ａは０〜４の整数であり、Ｒ^yは互いに独立に、水素原子、炭素数１〜１０の１価炭化水素基又はアシル基であり、Ｒ^yで示される基のうち、少なくとも１つは水素原子である。）
で表される基であり、Ｒ²は互いに独立に、炭素数１〜１２の置換又は非置換の１価炭化水素基、Ｒ³は互いに独立に、−ＯＸ
（式中、Ｘは水素原子又は炭素数１〜１２の置換又は非置換の１価炭化水素基である。）
で示される基、Ｒ¹は互いに独立に、上記Ｒ²及びＲ³の選択肢の中から選ばれる基である。ｑは互いに独立に０〜３の整数、ｒは互いに独立に０又は１であり、各末端においてｑ＋ｒは０〜３である。但し、一般式（２）及び一般式（４）は少なくとも１つの末端にＲ⁴を有する。ｎは１０〜５００の整数、ｍは１〜１０の整数である。］ As the component (A), organopolysiloxanes represented by the following general formulas (2) to (4) are preferable.

[In the above formulas (2) to (4), R ^{4 s} independently of each other from the following general formula (1)

(In the formula, R ^x is a divalent hydrocarbon group having 1 to 8 carbon atoms, a is an integer of 0 to 4, R ^y is independently a hydrogen atom, a monovalent carbon atom having 1 to 10 carbon atoms. (It is a hydrogen group or an acyl group, and at least one of the groups represented by R ^y is a hydrogen atom.)
R ² are independently of each other a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, R ³ are independently of each other, —OX
(In the formula, X is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms.)
And R ^1, independently of each other, is a group selected from the options of R ² and R ³ . q is independently an integer of 0 to 3, r is independently 0 or 1, and q + r is 0 to 3 at each end. However, the general formula (2) and the general formula (4) has an R ⁴ on at least one end. n is an integer of 10 to 500, and m is an integer of 1 to 10. ]

R ⁴ is independently a group represented by the above general formula (1), and preferred ranges and the like are the same as above.

R ² is independently of each other a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. Monovalent hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, Alkyl groups such as eicosyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; and carbon atoms of these groups Examples include halogenated alkyl groups and halogenated alkenyl groups in which some or all of the bonded hydrogen atoms are substituted with halogen atoms such as chlorine and fluorine. Of these, a methyl group is preferred industrially.

R ^{3 s} are independently of each other a group represented by —OX. X is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. X is preferably a hydrogen atom or an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group, and R ³ is a hydroxyl group, a methoxy group or an ethoxy group. Is preferred.

R ¹ is a group independently selected from the options of R ² and R ³ .

q is independently an integer of 0 to 3, r is independently 0 or 1, and q + r is 0 to 3 at each end. However, the general formula (2) and the general formula (4) has an R ⁴ on at least one end. The general formulas (2) to (4) preferably have at least one R ³ in the molecule, q is 1 or 2, more preferably 1, and more preferably q = 1 at both ends. . In the general formula (2), r at both ends is preferably 1.

  n is an integer of 10 to 500, preferably an integer of 20 to 200. If n is smaller than the lower limit, the effect of imparting flexibility or smoothness to the fiber may be insufficient. If n is larger than the upper limit, the organopolysiloxane after introduction of the polyoxyalkylene group The viscosity becomes high, and handling and emulsification may be difficult. m is an integer of 1-10. If m is larger than the upper limit, yellowing may occur easily.

（式中、Ｒ²、Ｒ³、Ｒ⁴、ｎ及びｍは上記と同じである。） Examples of the organopolysiloxane represented by the general formulas (2) to (4) include those represented by the following general formula.

(In the formula, R ² , R ³ , R ⁴ , n and m are the same as above.)

（式中、Ｒ²、Ｒ³、Ｒ⁴及びｎは上記と同じである。） Among these, organopolysiloxanes represented by the following general formula are preferable.

(Wherein R ² , R ³ , R ⁴ and n are the same as above)

（式中、Ｒ¹、Ｒ²、Ｒ³、ｎ、ｍ、ｑ及びｒは上記と同じである。Ｙは−Ｒ^y（ＮＨＣＨ₂ＣＨ₂）_aＮＨ₂で示される基である（Ｒ^y及びａは上述の通りである）。） Specific examples of the organopolysiloxanes represented by the general formulas (2) to (4) include organopolysiloxanes represented by the following general formulas (5) to (7).

(In the formula, R ¹ , R ² , R ³ , n, m, q and r are the same as above. Y is a group represented by —R ^y (NHCH ₂ CH ₂ ) _a NH ₂ (R ^y And a are as described above).)

  The amino group-containing organopolysiloxane represented by the general formula (5) can be easily obtained by a known synthesis method. For example, in the absence of a catalyst or in the presence of a catalyst such as an alkali metal hydroxide, both terminal hydroxy group-blocked dimethylpolysiloxane and 3-aminopropyldimethoxymethylsilane or N- (2-aminoethyl) -3-aminopropyldimethoxy It can be obtained by demethanol reaction with methylsilane.

  The amino group-containing organopolysiloxane represented by the general formula (6) or (7) can also be easily obtained by a known synthesis method. For example, in the presence of a catalyst such as an alkali metal hydroxide or tetramethylammonium hydroxide, a cyclic siloxane such as octamethylcyclotetrasiloxane and 3-aminopropyldiethoxymethylsilane or N- (2-aminoethyl) -3 -It can obtain by carrying out the equilibration reaction of the aminopropyl dimethoxymethylsilane or its hydrolyzate, and the compound selected from hexamethyldisiloxane etc. as another raw material.

（式中、Ｘは上記一般式（１０）で表される基であり、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、ｑ、ｒは上記と同じである。ｅ，ｉは互いに独立に１０〜５００の整数であり、ｅ＋ｉは１０〜５００、好ましくは２０〜２００である。ｆ，ｊは互いに独立に０〜２０の整数であり、ｆ＋ｊは１〜２０、好ましくは２〜１０である。ｇは１〜２００の整数、ｈは０〜２００の整数である。） The component (A) may have a branch in the organopolysiloxane skeleton. Examples of the organopolysiloxane having a branched structure include those represented by the following general formula (9).

(In the formula, X is a group represented by the general formula (10), and R ¹ , R ² , R ³ , R ⁴ , q, and r are the same as described above. E and i are each independently 10 E + i is 10 to 500, preferably 20 to 200. f and j are each independently an integer of 0 to 20, and f + j is 1 to 20, preferably 2 to 10. g is an integer of 1 to 200, and h is an integer of 0 to 200.)

  The organopolysiloxane of the present invention may use two or more types of organopolysiloxanes at the same time, and preferably has a viscosity at 25 ° C. of 50 to 50,000 mPa · s, more preferably 200 to 3,000 mPa · s, Preferably it is 300-2,000 mPa * s, Most preferably, it is 400-1,000 mPa * s. In the present invention, the viscosity is a value measured at 25 ° C. with a BM viscometer (for example, manufactured by Tokyo Keiki Co., Ltd.).

(B) Block polyisocyanate (B) A block polyisocyanate having two or more isocyanate groups in one molecule, and 50% or more of the isocyanate groups are blocked with a heat dissociable blocking agent. Or 2 or more types can be used in appropriate combination.

  As the component (B), various known block polyisocyanates can be used. The block polyisocyanate can be prepared by reacting various known polyisocyanate compounds with various known blocking agents.

  As polyisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-m-xylylene diisocyanate, tetramethylene-1,4-diisocyanate, pentamethylene-1 , 5-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene-1,6-diisocyanate, lysine diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatemethyl) -cyclohexane, 4,4, -dicyclohexyl A polyisocyanate which is a polymer of various diisocyanates such as methane diisocyanate and has an isocyanurate structure composed of these. Furthermore, various diisocyanates as described above, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, , 2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2 , 3-butanediol, 1,6-hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol 2-ethyl-hexanediol, 1,2-octanediol, 1,2-decane All, 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, glycerin, trimethylolpropane, pentaerythritol, polyester Polyisocyanate obtained by reacting various polyols such as polyol, polyether polyol, acrylic polyol and polyolefin polyol, polyisocyanate obtained by reacting polyisocyanate with water, polyisocyanate having biuret structure, as described above Examples thereof include polyisocyanates having an isocyanurate structure obtained by cyclization and trimerization of diisocyanate. In addition, polyisocyanates obtained by reacting various polyisocyanates as described above with various polyols as described above can also be used.

  Among them, tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene-1,6-diisocyanate, lysine diisocyanate, isophorone diisocyanate, 1,3 -Polymerizing diisocyanate monomers such as aliphatic, alicyclic diisocyanates such as bis (isocyanatomethyl) -cyclohexane, 4,4-dicyclohexylmethane diisocyanate, preferably aliphatic or alicyclic diisocyanates having 4 to 30 carbon atoms, A polyisocyanate compound having an isocyanate structure composed of this diisocyanate monomer is preferred. Of these, polyisocyanates having an isocyanurate structure composed of hexamethylene diisocyanate and polyisocyanates having an isocyanurate structure composed of hexamethylene diisocyanate are preferable from the viewpoint of weather resistance, availability, and the like. The polyisocyanate can contain a biuret group, a urea group, a uretdione group, a urethane group, an allophanate group, an oxadiazinetrione group, an iminooxadiazinedione group and the like at the same time.

  The thermally dissociable blocking agent that can be used in the present invention is a compound having at least one active hydrogen in the molecule, and can be used alone or in combination of two or more. Examples of the blocking agent include alcohol compounds, alkylphenol compounds, phenol compounds, active ethylene compounds, mercaptan compounds, acid amides, acid imides, imidazoles, urea compounds, oxime compounds, and amine compounds. , Imide compounds, pyrazole compounds and the like.

  More specifically, alcohol compounds such as methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, A mono- or dialkylphenol compound having an alkyl group having 4 or more carbon atoms as a substituent, for example, n-propylphenol, i-propylphenol, n-butylphenol, sec-butylphenol, t-butylphenol, n-hexyl Monoalkylphenols such as phenol, 2-ethylhexylphenol, n-octylphenol, n-nonylphenol, di-n-propylphenol, diisopropylphenol, isopropylcresol, isopropylcresol Dialkylphenols such as di-n-butylphenol, di-t-butylphenol, di-sec-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, di-n-nonylphenol, phenol, cresol, ethylphenol, styrene Alkylphenol compounds such as phenols such as fluorinated phenols and hydroxybenzoates, active ethylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate and acetylacetone, and mercaptan compounds such as butyl mercaptan and dodecyl mercaptan Acid amide compounds such as acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactone, γ-butyrolactam, and acid imides such as succinimide and maleic imide Compounds, imidazole compounds such as imidazole and 2-methylimidazole, urea compounds such as urea, thiourea and ethyleneurea, oxime compounds such as formamide oxime, acetal oxime, acetoxime, methyl ethyl ketone oxime and cyclohexanone oxime, diphenylamine Amine compounds such as aniline, carbazole, di-n-propylamine, diisopropylamine and isopropylethylamine, imine compounds such as ethyleneimine and polyethyleneimine, pyrazoles such as pyrazole, 3-methylpyrazole and 3,5-dimethylpyrazole System compounds and the like.

  Of these, active ethylene compounds, oxime compounds, and pyrazole compounds are preferable, and acetylacetone, diethyl malonate, methyl ethyl ketone oxime, cyclohexanone oxime, 3-methylpyrazole, and 3,5-dimethylpyrazole are more preferable.

  The reaction between the polyisocyanate and the blocking agent may be performed by a known method, and may be performed regardless of the presence or absence of a solvent. When using a solvent, it is necessary to use a solvent inert to the isocyanate group. In the blocking reaction, organometallic salts such as tin, zinc and lead, metal alcoholates and tertiary amines may be used as catalysts. The blocking reaction can be generally carried out at -20 to 150 ° C, preferably 0 to 100 ° C. If it exceeds 150 ° C., a side reaction may occur. On the other hand, if the temperature is too low, the reaction rate is low, which is disadvantageous. The block polyisocyanate may be such that 50% or more of the isocyanate groups are blocked with the above heat dissociable blocking agent, but it is preferably 75% or more blocked, particularly preferably 90% or more blocked. .

  The silicone composition of the present invention contains (A) 70 to 98 parts by mass of an organopolysiloxane and (B) 2 to 30 parts by mass of a blocked polyisocyanate. (A) 80-95 mass parts of organopolysiloxane and 5-20 mass parts of (B) block polyisocyanate are still more preferable. (A) Too much component, (B) If too little component, curability is low, washing durability when used as a fiber treatment agent is insufficient, (A) Too little component, (B) When there are too many components, the storage stability is insufficient.

  Various solvents can be used in the silicone composition of the present invention as necessary. Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, n-butyl acetate, cellosolve acetate, butanol, isopropyl alcohol, toluene, dipropylene glycol monomethyl ether and the like. These solvents can be used singly or in appropriate combination of two or more. The amount of the solvent is preferably 0 to 50% by mass in the silicone composition. The silicone composition of this invention can be manufactured by mixing the said (A) component, (B) component, and various solvents uniformly as needed.

  Furthermore, it is preferable that it is the reaction material which one or more NH group contained in the organopolysiloxane of (A) component and the isocyanate group of (B) component reacted. The reaction method is not particularly limited and may be a conventionally known method. For example, the reaction can be performed by heating during mixing. The temperature during the reaction is not particularly limited, but is preferably 0 ° C to 200 ° C, and more preferably 50 ° C to 150 ° C. Although reaction time is not specifically limited, Although it adjusts suitably with reaction temperature, 30 minutes-5 hours are preferable.

[Silicone emulsion composition]
The silicone composition of the present invention can be emulsified with a surfactant such as a nonionic, anionic surfactant or cationic surfactant to form a silicone emulsion composition containing the same. 10-50 mass% is preferable and the compounding quantity of the silicone composition in a silicone emulsion composition has more preferable 20-40 mass%. The emulsification method will be described later.

  The silicone composition of the present invention is a curable silicone composition, is excellent in low-temperature curability, and can impart good flexibility to various fibers or textiles. Furthermore, it has excellent washing durability. Therefore, the silicone composition of the present invention is useful as a fiber treatment agent. 0.01-50 mass% is preferable and, as for the compounding quantity of the silicone composition in a fiber treatment agent, 0.1-40 mass% is more preferable. In the case of treating the fiber, it may be used after diluting, and the blending amount of the silicone composition in the diluted fiber treating agent for treating the fiber is preferably 0.01 to 5% by mass as the solid content, 0.1 to 0.1%. 0.5 mass% is more preferable.

  The fiber treatment agent of the present invention is effective not only for natural fibers such as cotton, silk, hemp, wool, angora, and mohair, but also for synthetic fibers such as polyester, nylon, acrylic, and spandex, and fiber products using these. It is. Also, there are no restrictions on the form and shape, and not only the shape of raw materials such as staples, filaments, tows and yarns, but also various processing forms such as woven fabrics, knitted fabrics, stuffed cotton, non-woven fabrics, paper, sheets, films, etc. Is also a processable object of the fiber treatment composition of the present invention.

  When the composition of the present invention is used as a fiber treating agent, it is dissolved in an organic solvent such as toluene, xylene, n-hexane, n-heptane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, mineral terpene, etc. Alternatively, it is processed into a fiber product, or processed into a fiber or a fiber product with a surfactant such as a nonionic, anionic surfactant, or cationic surfactant. These emulsifiers are not particularly limited. For example, nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, sorbitan alkylate, polyoxyethylene sorbitan alkylate, alkylbenzene sulfonate, alkyl phosphoric acid It can be selected from anionic emulsifiers such as salts, cationic emulsifiers such as quaternary ammonium salts and alkylamine salts, and amphoteric emulsifiers such as alkylbetaines and alkylimidazolines. 5-50 mass parts is preferable with respect to 100 mass parts of (A) organopolysiloxane, More preferably, the usage-amount of these emulsifiers is 10-30 mass parts. The amount of water used for emulsification may be any amount, but is generally such that the organopolysiloxane pure concentration is 5 to 60% by mass, preferably 10 to 40% by mass. It is an amount.

  In order to emulsify the fiber treatment agent, the organopolysiloxane and the surfactant in the present invention may be mixed and emulsified with an emulsifier such as a homomixer, a homogenizer, a colloid mill, or a line mixer. As a processing method, it adjusts to a desired density | concentration as the melt | dissolution or emulsion by the organic solvent of a silicone composition, and it makes it adhere to a fiber by means, such as immersion, a spray, and a roll coat. The amount of adhesion varies depending on the type of fiber and is not particularly limited, but it is generally in the range of 0.01 to 10% by mass in terms of pure organopolysiloxane with respect to the fabric. Then, it may be dried by hot air blowing, heat treatment or the like. Although depending on the type of fiber, the immersion time may be 1 to 5 minutes, the drying temperature and the drying time may be 100 to 200 ° C. and 1 to 15 minutes, respectively.

  The silicone composition of the present invention can be used for various applications in addition to fiber processing applications, such as coatings, adhesives, sealing agents, inks, papers and other impregnating agents, and surface treatments. Can do. In this case, additives can be used as necessary. Examples of additives include anti-wrinkle agents, flame retardants, antistatic agents, heat-resistant agents and other fiber agents, antioxidants, ultraviolet absorbers, pigments, metal powder pigments, rheology control agents, curing accelerators, and deodorants. And antibacterial agents. These additives can be used singly or in appropriate combination of two or more.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, unless otherwise specified, “%” in the composition indicates mass%, and the “part” ratio indicates mass part.

In addition, the measuring method in the following example is the following method.
The average molecular weight is a polystyrene-based number average molecular weight measured by gel permeation chromatography (hereinafter referred to as GPC) using the following apparatus.
Equipment: Tosoh Corporation HLC-802A
Column: Tosoh Corporation G1000HXL × 1 G2000HXL × 1 G3000HXL × 1 Carrier: Tetrahydrofuran Detection method: differential refractometer

The viscosity is a value measured at 25 ° C. with a BM viscometer (manufactured by Tokyo Keiki Co., Ltd.).
¹ HNMR was measured with a 400 MHz FT-NMR apparatus (manufactured by JEOL Ltd.) in deuterated chloroform solvent.

[Synthesis Example 1]
A separable flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube and a dropping funnel was placed in a nitrogen atmosphere, 600 parts of hexamethylene diisocyanate was charged, and the temperature in the reactor was kept at 70 ° C. with stirring. The isocyanuration catalyst tetramethylammonium capriate was added, and when the reaction rate reached 40%, phosphoric acid was added to stop the reaction. After the reaction solution was filtered, unreacted hexamethylene diisocyanate was removed using a thin film evaporator. The resulting polyisocyanate had a viscosity at 25 ° C. of 2,500 mPa · s and a number average molecular weight of 680.
The reaction rate of isocyanurate formation is the peak area corresponding to the molecular weight of isocyanurate in the total of the peak area corresponding to the molecular weight corresponding to unreacted hexamethylene diisocyanate and the peak area corresponding to the molecular weight corresponding to isocyanurate obtained by the GPC measurement. The ratio was expressed as a reaction rate.

[Synthesis Example 2]
A reactor similar to Synthesis Example 1 was charged with 100 parts of the isocyanurate obtained in Synthesis Example 1, 13 parts of polypropylene diol, and butyl acetate as a solvent so that the final block polyisocyanate component concentration was 90%. Hold at 70 ° C. for 3 hours. Thereafter, 50 parts of 3,5-dimethylpyrazole was added, and it was confirmed that the characteristic absorption of the isocyanate group disappeared in the infrared spectrum. The average molecular weight of the obtained block polyisocyanate was 1,200.

[Synthesis Example 3]
A reactor similar to Synthesis Example 1 was charged with 100 parts of the isocyanurate obtained in Synthesis Example 1, 13 parts of polypropylene diol, and butyl acetate as a solvent so that the final block polyisocyanate component concentration was 90%. Hold at 70 ° C. for 3 hours. Thereafter, 45 parts of methyl ethyl ketone oxime was added, and it was confirmed that there was no characteristic absorption of isocyanate groups in the infrared spectrum. The average molecular weight of the obtained block polyisocyanate was 1,100.

[Synthesis Example 4]
A reactor similar to Synthesis Example 1 was charged with 100 parts of the isocyanurate obtained in Synthesis Example 1, 13 parts of polypropylene diol, and butyl acetate as a solvent so that the final block polyisocyanate component concentration was 90%. Hold at 70 ° C. for 3 hours. Thereafter, 83 parts of diethyl malonate was added, and it was confirmed by infrared spectrum that there was no characteristic absorption of isocyanate groups. The average molecular weight of the obtained block polyisocyanate was 1,280.

[Example 1]
Into a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube, organopolysiloxane represented by the following formula (A) (molecular weight 4,066, amine equivalent: 1,010 g / mol) 95. 0 parts and 5.0 parts of the blocked polyisocyanate obtained in Synthesis Example 2 were added, and the mixture was stirred in nitrogen atmosphere at 100 ° C. for 2 hours to obtain a silicone composition.

[Example 2]
A silicone composition was prepared in the same manner as in Example 1, except that the organopolysiloxane represented by the above formula (A) was changed to the organopolysiloxane represented by the following formula (B).

[Example 3]
A silicone composition was prepared in the same manner as in Example 1, except that the organopolysiloxane represented by the above formula (A) was changed to the organopolysiloxane represented by the following formula (C).

[Example 4]
A silicone composition was prepared in the same manner as in Example 1 except that the block polyisocyanate obtained in Synthesis Example 2 was changed to the block polyisocyanate obtained in Synthesis Example 3.

[Example 5]
A silicone composition was prepared in the same manner as in Example 1 except that the block polyisocyanate obtained in Synthesis Example 2 was changed to the block polyisocyanate obtained in Synthesis Example 4.

[Example 6]
95.0 parts of the organopolysiloxane represented by the above formula (A) (molecular weight 4066, amine equivalent: 1010 g / mol) and 5.0 parts of the block polyisocyanate obtained in Synthesis Example 2 were stirred at 25 ° C. for 30 minutes, A silicone composition was obtained.

[Example 7]
A silicone composition was prepared in the same manner as in Example 1 except that the organopolysiloxane represented by the above formula (A) was changed to 90.0 parts and the blocked polyisocyanate obtained in Synthesis Example 2 was changed to 10.0 parts. did.

[Example 8]
A silicone composition was prepared in the same manner as in Example 1 except that 97.0 parts of the organopolysiloxane represented by the above formula (A) and 9 parts of the blocked polyisocyanate obtained in Synthesis Example 2 were changed to 3.0 parts. did.

[Comparative Example 1]
A silicone composition was prepared in the same manner as in Example 1, except that the organopolysiloxane represented by the above formula (A) was changed to 99.0 parts and the blocked polyisocyanate obtained in Synthesis Example 2 was changed to 1.0 part. did.

[Comparative Example 2]
A silicone composition was prepared by the same composition and method as in Comparative Example 1 except that the organopolysiloxane represented by the above formula (A) was changed to the organopolysiloxane represented by the above formula (B).

[Comparative Example 3]
A silicone composition was prepared by the same composition and method as in Comparative Example 1, except that the organopolysiloxane represented by the above formula (A) was changed to the organopolysiloxane represented by the above formula (C).

[Comparative Example 4]
A silicone composition was prepared by the same composition and method as in Comparative Example 1 except that the block polyisocyanate obtained in Synthesis Example 2 was changed to the block polyisocyanate obtained in Synthesis Example 3.

[Comparative Example 5]
A silicone composition was prepared by the same composition and method as in Comparative Example 1 except that the block polyisocyanate obtained in Synthesis Example 2 was changed to the block polyisocyanate obtained in Synthesis Example 4.

[Evaluation test]
1. Curability 2 g of the silicone composition was weighed in an aluminum petri dish having a diameter of 6 cm and heated at 120 ° C. for 15 minutes. The case where the entire composition was cured was designated as “A”, the case where only a part of the composition was cured was designated as “B”, and the case where the entire composition was uncured was designated as “C”. The results are shown in Table 1.

2. Storage stability 5 g of the silicone composition was filled in a 25 mL glass bottle and allowed to stand at 25 ° C. for 1 day, and then the appearance was observed. Those having a good appearance were rated “good”, and those having thickened or gelled were “bad”. The results are shown in Table 1.

[Example 9]
60 g of the silicone composition obtained in Example 1 and 10 g of polyoxyethylene alkyl ether (Emulgen 1108: manufactured by Kao) were mixed at 2000 rpm for 20 minutes using a homomixer, and emulsified and dispersed in 20 g of water. Thereafter, it was diluted with 110 g of water to obtain an emulsion composition.

[Example 10]
An emulsion composition was prepared by the same composition and method as in Example 9, except that the silicone composition obtained in Example 1 was changed to the silicone composition obtained in Example 2.

[Example 11]
An emulsion composition was prepared by the same composition and method as in Example 9, except that the silicone composition obtained in Example 1 was changed to the silicone composition obtained in Example 3.

[Example 12]
An emulsion composition was prepared by the same composition and method as in Example 9, except that the silicone composition obtained in Example 1 was changed to the silicone composition obtained in Example 4.

[Example 13]
An emulsion composition was prepared by the same composition and method as in Example 9, except that the silicone composition obtained in Example 1 was changed to the silicone composition obtained in Example 5.

[Example 14]
An emulsion composition was prepared by the same composition and method as in Example 9, except that the silicone composition obtained in Example 1 was changed to the silicone composition obtained in Example 6.

[Example 15]
An emulsion composition was prepared by the same composition and method as in Example 9, except that the silicone composition obtained in Example 1 was changed to the silicone composition obtained in Example 7.

[Example 16]
An emulsion composition was prepared by the same composition and method as in Example 9, except that the silicone composition obtained in Example 1 was changed to the silicone composition obtained in Example 8.

[Comparative Example 6]
An emulsion composition was prepared by the same composition and method as in Example 9, except that the silicone composition obtained in Example 1 was changed to the silicone composition obtained in Comparative Example 1.

[Comparative Example 7]
An emulsion composition was prepared by the same composition and method as in Example 9, except that the silicone composition obtained in Example 1 was changed to the silicone composition obtained in Comparative Example 2.

[Comparative Example 8]
An emulsion composition was prepared by the same composition and method as in Example 9, except that the silicone composition obtained in Example 1 was changed to the silicone composition obtained in Comparative Example 3.

[Comparative Example 9]
An emulsion composition was prepared by the same composition and method as in Example 9, except that the silicone composition obtained in Example 1 was changed to the silicone composition obtained in Comparative Example 4.

[Comparative Example 10]
An emulsion composition was prepared by the same composition and method as in Example 9, except that the silicone composition obtained in Example 1 was changed to the silicone composition obtained in Comparative Example 5.

[Comparative Example 11]
An emulsion composition was prepared by the same composition and method as in Example 9, except that the silicone composition obtained in Example 1 was changed to the organopolysiloxane represented by the above formula (A).

[Evaluation test]
Each emulsion composition was subjected to the following evaluation test. The results are shown in Table 2.
3. Flexibility Ion exchange water was added to the emulsion composition and diluted to a solid content of 0.5% to prepare a test solution. A polyester / cotton broad cloth (65% / 35%, manufactured by Tanigami Shoten) was immersed in the test solution for 1 minute, then squeezed with a roll under the condition of a squeezing rate of 100%, dried at 100 ° C. for 2 minutes, and further A heat treatment was performed at 150 ° C. for 2 minutes to prepare a treated cloth for flexibility evaluation. Three panelists touched the treated cloth, and the flexibility was evaluated according to the following criteria.
<Evaluation criteria>
A: The touch feeling is very good.
B: The touch feeling is good.
C: Uncomfortable to touch.

4). Washing durability Ion exchanged water was added to the emulsion composition and diluted to a solid content of 2% to prepare a test solution. A polyester / cotton broad cloth (65% / 35%, manufactured by Tanigami Shoten Co., Ltd.) was immersed in the test solution for 10 seconds, then squeezed with a roll under the condition of a squeezing rate of 100%, and dried at 130 ° C. for 2 minutes. Thereafter, the treated fabric was washed once by a washing machine by a method based on JIS L0217 103. The amount of silicone remaining on the fiber surface after one wash was measured with a fluorescent X-ray analyzer (manufactured by Rigaku). The residual rate (%) was calculated in comparison with the case where washing was not performed.

  As shown in Table 1, the silicone composition of the present invention is excellent in low-temperature curability and storage stability. In addition, as shown in Table 2, the fiber treatment agent using the silicone composition of the present invention can impart good flexibility to the fiber and is excellent in washing durability.

  The silicone composition of the present invention has excellent low-temperature curability, and by using this composition as a fiber treatment agent, good flexibility can be imparted to the fiber. Moreover, it is excellent in washing durability and can be used as a highly durable binder resin.

Claims (6)

(A) 70 to 98 parts by mass of an organopolysiloxane having a group represented by the following general formula (1) at the molecular end or side chain;

(In the formula, R ^x is a divalent hydrocarbon group having 1 to 8 carbon atoms, a is an integer of 0 to 4, R ^y is independently a hydrogen atom, a monovalent carbon atom having 1 to 10 carbon atoms. (It is a hydrogen group or an acyl group, and at least one of the groups represented by R ^y is a hydrogen atom.)
(B) A silicone composition containing 2 to 30 parts by mass of a blocked polyisocyanate having 2 or more isocyanate groups in one molecule and 50% or more of the isocyanate groups blocked with a heat dissociable blocking agent.   The silicone composition according to claim 1, which is a reaction product of one or more NH groups contained in the organopolysiloxane of component (A) and an isocyanate group of component (B).   The silicone composition according to claim 1 or 2, wherein the component (B) is a block polyisocyanate having a polyisocyanate structure composed of an aliphatic and / or alicyclic diisocyanate monomer.   The silicone composition according to any one of claims 1 to 3, wherein the thermally dissociable blocking agent of component (B) is a compound selected from the group consisting of oxime compounds, pyrazole compounds and active ethylene compounds.   The silicone emulsion composition containing the silicone composition of any one of Claims 1-4.   The fiber treatment agent containing the silicone composition of any one of Claims 1-4.