JP2002037842A - Ultraviolet curing siloxane modified polyurethane, and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet curing polyurethane solving poor curing and the various problems resulting from a poor curing property when using a curing agent such as polyisocyanate or the like. SOLUTION: A urethane polymer has a polysiloxane segment having an unsaturated group in a side chain derived from the polysiloxane compound. (m or n is an integer from which a molecular weight is set to 3,200).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a UV-curable siloxane-modified polyurethane and a method for producing the same.
Excellent heat resistance, high hardness, cold resistance, solvent resistance, chemical resistance, weather resistance, stain resistance, lubricity, migration resistance, water repellency, oil repellency, mechanical strength, abrasion resistance, flexibility Ultraviolet-curable siloxane-modified polyurethane and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, polyurethane is excellent in various physical properties such as abrasion resistance, adhesiveness, flexibility, chemical resistance and the like, and is also suitable for various processing methods. Polyurethanes are widely used as binders, films, and sheet-like materials, and have been proposed for various uses. In addition, polyurethane is a general term for polyurethane, polyurea, and polyurethane-polyurea.

[0003] These polyurethanes are basically composed of a polyol component, a polyisocyanate component, a polyamine component,
Furthermore, it is obtained by reacting a chain extender component as required, and polyurethanes having various performances are provided depending on the type and combination of each component. In addition, various cross-linking systems have been proposed in order to improve the properties of polyurethane for the above-mentioned various uses.

[0004]

Polyurethanes are often used by using various crosslinking agents in combination and curing by heating. For example, when an isocyanate group-containing compound is used as a crosslinking agent, curing is said to proceed at room temperature,
Practically, problems such as pot life (pot life) and problems such as poor curing due to the reaction of moisture or other impurities with isocyanate groups are likely to occur. As a result, there has been a problem that various properties such as heat resistance, adhesion to a substrate, and coating film strength cannot be sufficiently exhibited.

Accordingly, an object of the present invention is to introduce an ultraviolet curing function in place of curing using a cross-linking agent which causes the above-mentioned problems, and to provide heat resistance, cold resistance, high hardness, lubricity, migration resistance, and repellency. Excellent physical properties such as water-repellency, oil-repellency, mechanical strength, adhesiveness, abrasion resistance, flexibility, etc., as well as solvent resistance, chemical resistance, weather resistance,
An object of the present invention is to provide an ultraviolet-curable siloxane-modified polyurethane having excellent properties such as anti-staining properties.

[0006]

The above object is achieved by the present invention described below. That is, a first aspect of the present invention is to react a polysiloxane compound having an unsaturated group represented by the following general formula (1) and an active hydrogen-containing group, a polyisocyanate, a polyol or a polyamine, and a chain extender. The content of the obtained polysiloxane segment derived from the polysiloxane compound in the molecule is 1 to 75% by weight.
And a UV-curable siloxane-modified polyurethane having a weight average molecular weight of 5,000 to 500,000. (However, R in the formula represents a methyl group or a phenyl group, and R ₁
Represents nothing or a divalent organic group, R ₂ represents a hydrogen atom or a hydrocarbon group, X represents an active hydrogen-containing group, and m and n each represent an integer of 1 to 300. A second aspect of the present invention is that at least one unsaturated group is provided on a side chain;
Production of an ultraviolet-curable siloxane-modified polyurethane characterized by reacting a polysiloxane compound having at least one active hydrogen-containing group at a molecular chain terminal and / or a side chain, a polyisocyanate, a polyol or a polyamine, and a chain extender. Is the way.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments of the present invention. The polyurethane of the present invention is characterized in that it has a polysiloxane segment having an unsaturated group curable by ultraviolet rays in a side chain in a molecular chain. As a result, there is no curing failure because it is instantaneously cured by UV irradiation, heat resistance, cold resistance, high hardness, lubricity, migration resistance, water repellency, oil repellency, mechanical strength, adhesion,
It is possible to produce a cured polyurethane material having excellent properties such as abrasion resistance and flexibility, and excellent properties such as solvent resistance, chemical resistance, weather resistance, and stain resistance.

The ultraviolet-curable siloxane-modified polyurethane of the present invention comprises a polysiloxane compound having an active hydrogen-containing group at both ends and at least one unsaturated group in a side chain represented by the general formula (1). , Polyisocyanate,
It can be obtained by reacting a polyol or polyamine and, if necessary, a chain extender. In the ultraviolet-curable siloxane-modified polyurethane of the present invention, the polysiloxane compound is introduced as a polysiloxane segment in the polyurethane chain, and an unsaturated group that makes the polyurethane ultraviolet-curable is introduced as a side chain of the polysiloxane segment. ing.

In the present invention, even if a polysiloxane compound other than the polysiloxane compound represented by the above general formula (1) is used, the polyurethane can be modified into an ultraviolet curing type. Such a polysiloxane compound is
All have at least one unsaturated group in the side chain in the same manner as the above-mentioned polysiloxane compound, but have at least one active hydrogen-containing group in one terminal and / or in the side chain. Is different. In this case, the polysiloxane segment is introduced into the molecular chain or at the terminal of the molecular chain.

The polysiloxane compound having an active hydrogen-containing group and an unsaturated group used for producing an ultraviolet-curable siloxane-modified polyurethane in the present invention includes the following compounds as typical compounds. Examples of the active hydrogen-containing group in the present invention include an amino group,
Examples include a hydroxyl group, a carboxyl group, a mercapto group, and an epoxy group.

(1) Amino-modified unsaturated group-containing polysiloxane compound

(2) Hydroxyl-modified polysiloxane compound

[0013]

(3) Carboxyl-modified polysiloxane compound

The polysiloxane compounds having a reactive functional group and an unsaturated group listed above are examples of preferred compounds used in the present invention, and the present invention is not limited to these exemplified compounds. . Therefore, not only the above-mentioned exemplified compounds but also other compounds which are currently commercially available and can be easily obtained from the market can be used in the present invention.

As the polyisocyanate used in the present invention, any conventionally known polyisocyanate can be used. Preferred are, for example, 1,6-hexamethylene diisocyanate (HMDI), 2,2,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, methylene diisocyanate, isopropylene diisocyanate, lysine diisocyanate,
Aliphatic polyisocyanate compounds such as 1,5-octylene diisocyanate and dimer acid diisocyanate;
4,4'-dicyclohexylmethane diisocyanate,
Isophorone diisocyanate (IPDI), hydrogenated tolylene diisocyanate, methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4 '
-Diisocyanate, methylcyclohexane-2,4
Alicyclic polyisocyanate compounds such as (or 2,6) -diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane, and 4,4'-methylenebis (cyclohexylisocyanate);

2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, xylylene diisocyanate (XDI),
Triphenylmethane triisocyanate, tris (4-
Phenyl isocyanate) thiophosphate, tolidine diisocyanate, p-phenylene diisocyanate,
Aromatic polyisocyanates such as diphenyl ether diisocyanate and diphenyl sulfone diisocyanate; and araliphatic polyisocyanate compounds such as xylylene diisocyanate, tetramethyl xylylene diisocyanate, and cyclohexane phenylene diisocyanate.

In addition to the above, organic polyisocyanate compounds having an adduct, such as MDI, TDI,
Adducts obtained by reacting HMDI, XDI, IPDI, etc. with dihydric or trihydric polyhydric alcohols; HMDI, IP
Burettes such as DI; ureton-on such as TDI; isocyanurates such as TDI, HMDI and IPDI. The polyisocyanates exemplified above may be used alone or in combination of two or more. Further, polyurethane prepolymers obtained by reacting these polyisocyanates with low molecular weight polyols or polyamines so as to be terminal isocyanates may also be used. it can.

The polyol or polyamine used in the present invention preferably has a molecular weight in the range of 200 to 8,000. Examples of the high molecular weight polyol compound having a hydroxyl group at a terminal include polyether polyols such as polytetramethylene glycol ether, polyethylene glycol ether, polypropylene glycol ether, polyethylene-propylene glycol ether, polytetramethylene ether glycol, and polyhexamethylene ether glycol. Polyester polyols such as condensation-based polyester polyols, polycarbonate polyols, lactone-based polyester polyols such as polycaprolactone polyol and polyvalerolactone polyol; polyacryl polyols, polyolefin polyols, polybutadiene polyols, and fat-modified polyols. Examples of the low-molecular-weight polyol include low-molecular-weight polyols, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sugar alcohols such as sucrose, glucose, and fructose.

Examples of the above-mentioned condensed polyester polyols include dibasic acids (for example, itaconic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid,
Maleic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, tartaric acid, oxalic acid, malonic acid, pimelic acid, suberic acid, curtaconic acid, azelaic acid, 1,4
-Cyclohexyldicarboxylic acid, [alpha] -hydromuconic acid, [beta] -hydromuconic acid, [alpha] -butyl- [alpha] -ethylglutaric acid, [alpha], [beta] -diethylsuccinic acid, etc.) or anhydrides and glycols (e.g., ethylene glycol, diethylene glycol). , Triethylene glycol, dipropylene glycol, tripropylene glycol, 1,2
-Propanediol, 1,3-propanediol, 1,
2-butanediol, 1,3-butanediol, 1,4
-Butanediol, 1,5-pentanediol, 1,6
Aliphatic glycols such as -hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol and neopentyl glycol; bishydroxymethylcyclohexane, cyclohexane-1,4-diol An alicyclic glycol such as xylylene glycol; an aliphatic glycol having 1 to 1 carbon atoms;
About 8 alkyldialkanolamines such as alkyldiethanolamine), for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate and the like.

Other polyols include, for example, active hydrogen-containing groups such as ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, and xylylenediamine.
With at least one compound selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, amylene oxide, alkylene oxides such as tetrahydrofuran, alkyl glycidyl ethers such as methyl glycidyl ether, and aryl glycidyl ethers such as phenyl glycidyl ether. Compounds obtained by addition polymerization by a known method are exemplified. As the high molecular weight polyetherester diol compound, for example, an ether group-containing diol or a mixture of this and another glycol is reacted with the above-mentioned dibasic acid or its anhydride, or an alkylene oxide is added to polyester glycol. Obtained by reacting, for example, poly (tetramethylene ether)
Adipate and the like. The polyol exemplified above is
One type or a combination of two or more types can be used. Further, the polyol may have an unsaturated group.

The polyamine used in the present invention is preferably an aliphatic polyamine. As the aliphatic polyamine, for example, ethylenediamine, diaminopropane, diaminobutane, hexamethylenediamine, trimethylhexamethylenediamine, diaminopropylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, Bis-aminopropylpiperazine, polyoxyethylenediamine, polyoxypropylenediamine, polyoxyethylenepropylenediamine,
Polyoxyethylene triamine, polyoxypropylene triamine, isophorone diamine, diallylamine,
1,3-bisaminomethylcyclohexane, 4,4-diaminocyclohexylmethane, diaminobenzene, m-
Hydrazines such as hydrazine, carbodihydrazide, adipic dihydrazide, sebacic dihydrazide, and phthalic dihydrazide, such as xylene diamine, 1,4-diaminocyclohexaneisophorone diamine, and the like. These can be used alone or in combination of two or more.

The chain extender used in the present invention includes, for example, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol,
3-propanediol, 1,2-butanediol, 1,
3-butanediol, 1,4-butanediol, 1,5
-Pentanediol, 1,6-hexanediol, 3-
Compounds such as aliphatic glycols such as methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, glycerin / monoallyl ether, and acetylene-containing diol; bishydroxymethylcyclohexane; Cyclohexane-
Examples include alicyclic glycol compounds such as 1,4-diol, aromatic glycol compounds such as xylylene glycol, and compounds such as alkyldialkanolamines having about 1 to 18 carbon atoms such as alkyldiethanolamine. Examples of polyhydric alcohol compounds include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, tris- (2-hydroxyethyl) isocyanurate, 1,1,1-trimethylolethane, and 1,1,1. -Trimethylolpropane. These can be used alone or in combination of two or more.

The ultraviolet-curable siloxane-modified polyurethane of the present invention can be obtained by reacting each of the above-mentioned components in a solvent or without using a solvent according to a usual polyurethane production method. Therefore, in the present invention, a characteristic of the method for producing a polyurethane is to use a polysiloxane compound represented by the general formula (1) and other polysiloxane compounds having a functional group having active hydrogen and an unsaturated group. It is to be.

In the present invention, the above-mentioned polysiloxane compound is used in an amount such that the content of the polysiloxane segment introduced from the compound in the obtained polyurethane is 1 to 75% by weight, preferably 1 to 60% by weight. used. When the content of the segment is less than 1% by weight, adhesion to a substrate, heat resistance, chemical resistance, stain resistance, lubricity, water repellency,
Insufficient properties such as oil repellency, 75% by weight
If the ratio exceeds the above range, deformation of the substrate or the properties of the polysiloxane segment becomes stronger due to steric hindrance due to a high crosslinking density, resulting in a decrease in adhesion to the substrate, a decrease in mechanical strength, abrasion resistance and the like. Further, it is not preferable because long-term solution stability is impaired. Also, the content of unsaturated groups in the polyurethane,
0.001 to 10 meq (milliequivalent) / g (polymer)
Is preferable. If it is less than 0.001 meq / g, not only the strength of the coating after ultraviolet curing becomes insufficient, but also the adhesion to the substrate may be poor. On the other hand, if it exceeds 10 meq / g, the ultraviolet-cured coating film is hard and brittle, and the substrate is undesirably deformed. In addition, a high crosslink density may result in a decrease in physical properties of the coating. The weight average molecular weight (measured by GPC, standard polystyrene conversion) of polyurethane is
5,000-500,000 is preferred.

The UV-curable siloxane-modified polyurethane of the present invention has an unsaturated group in the molecule, so that it can be cross-linked by ultraviolet rays or the like, and has excellent adhesiveness to various materials and heat resistance. Excellent in hardness, cold resistance, solvent resistance, chemical resistance, weather resistance, stain resistance, lubricity, migration resistance, water repellency, oil repellency, mechanical strength, abrasion resistance, flexibility It is useful for various paints, various ink binders, various sheet-like coating agents, and resist materials. Hereinafter, the use for an ultraviolet curable material will be described.

The ultraviolet-curable siloxane-modified polyurethane of the present invention can be used as a single component, but a crosslinking agent (curing agent) or a reactive diluent may be used in combination to further improve the physical properties. The curing agent is not particularly limited, and examples thereof include a polyfunctional acrylic monomer having an unsaturated group, a polyisocyanate, a melamine resin, an epoxy resin, and the like, and derivatives thereof.

Examples of the reactive diluent include radically polymerizable monofunctional acrylate compounds, polyfunctional acrylate compounds, and cationic polymerizable compounds. Examples of the radical polymerizable monofunctional acrylate compound include, for example, tetrahydrofurfuryl (meth) acrylate,
Examples thereof include 2-ethylhexyl (meth) acrylate, methoxyethyl (meth) acrylate, N-vinylpyrrolidone, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and diethylene glycol di (meth) acrylate. Examples of the polyfunctional acrylate compound include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol hexa (meth) acrylate, trimethylolpropane di (meth) acrylate, and pentatrislittetra (meth) acrylate.
Acrylate and the like. Examples of the cationic polymerizable diluent include an epoxy compound, an okitacene compound, a vinyl ether compound and the like.

Examples of usable organic solvents include, for example, methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, butyl acetate, acetone, Cyclohexane, tetrahydrofuran, dioxane, methanol, ethanol,
Isopropyl alcohol, butanol, toluene, xylene, dimethylformamide, dimethylsulfoxide,
Methyl cellosolve, ethyl cellosolve, butyl cellosolve, water and the like are mentioned, and a preferable solvent is a solvent that dissolves polyurethane. The solubility of the polyurethane is determined by a hard segment composed of a combination of a polyisocyanate and a chain extender.

The photopolymerization initiator is not particularly limited, but is preferably one that generates a radical by light and reacts with the polymerizable unsaturated compound. For example, benzophenone, acetophenone, benzoin, benzoin isobutyl ether, benzoin isopropyl ether, benzoin ethyl ether, 2,4-dimethylthioxanthone, 2-chlorothioxanthone, ethylanthraquinone, 4,4'-bisdimethylaminobenzophenone,
-Hydroxy-2-methyl-1-phenylpropane-1
-One, benzyldimethyl ketal and the like.
Examples of the cationic polymerization initiator include a diazonium salt type compound, a sulfonium salt type compound, and an iodonium salt type compound. One or more of these photopolymerization initiators may be used in combination.

In order to control the thermal polymerization reaction, a polymerization inhibitor such as orthonitrotoluene, hydroquinone, hydroquinone monomethyl ether, copper chloride and the like can be added. Further, as other additives, an antioxidant, a light stabilizer, a paint additive, a function-imparting agent, and the like can be appropriately compounded according to various uses.

[0032]

Next, the present invention will be described more specifically with reference to examples and comparative examples. The parts or percentages in the text are based on weight.

Examples 1 to 5 and Comparative Examples 1 to 4 A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blowing pipe and a manhole was replaced with nitrogen gas. A predetermined amount of a siloxane component, a polyol component, a chain extender, and a solvent were added, and the solvent was further added to dissolve uniformly, and the solution concentration was adjusted to 30%. Subsequently, a predetermined amount of diisocyanate was added and reacted at 80 ° C. until the viscosities (measured by a B-type viscometer) shown in Tables 1 and 2 were obtained. Tables 1 and 2 show the raw material composition and properties of polyurethane (PU) and physical properties measured using a film (uncrosslinked) formed from a solution of each polyurethane according to JIS K6301. The properties of Comparative Examples 2 to 4 were 1010 when the additives described in Table 2 were added (the fluororesin powder had an average particle size of 5 μm (Rublon L2 manufactured by Daikin Industries, Ltd.). (Polyethylene wax) has a molecular weight of 2,000 and a melting point of 120 ° C.
(Mitsui Chemicals, Mitsui High Wax 210) was used. ). The content of the polysiloxane segment in the polyurethane was measured by infrared spectroscopy according to JIS K0117, and the content of the unsaturated group was measured by the element number method such as JIS K0070.

The structure of the obtained polymer was confirmed by IR absorption spectrum. FIG. 1 shows an IR spectrum of the polyurethane of Example 3. At 2,270 cm ⁻¹ , characteristic absorption due to isocyanate groups is not freely recognized, and
At 1,090 cm ^-1 , the characteristic absorption based on -Si-O-Si- was 1,400 cm ^-1 , 960 cm ^-1 and 1,590 cm ^-1.
At cm ^-1 , characteristic absorption based on -C = C- was confirmed.

[0035]

[0036]

[0037]

Compound A in the table is a polysiloxane compound having the following structure.

Use Examples The polyurethane solutions (1) of Examples 1-4 and Comparative Examples 1-4
00 parts), hard coat paints 1-8 for plastics having the compositions shown in Tables 3 and 4 were prepared. After applying each coating composition to a surface of a 100 μm-thick polyethylene terephthalate film (manufactured by Toray Industries, Inc.) so that the thickness after drying becomes 20 μm by a known method, the solvent is dried in a dryer. I let it. A peak illuminance of 382 mw / cm ² using a metal halide lamp from above the application surface of the dried film sheet using paints 1 to 4 and paints 7 and 8, and an integrated light quantity of 4
Irradiation was performed at an irradiation intensity of 15 mJ / cm ² , and crosslinked to prepare a film sheet. When paints 5 and 6 were used, they were applied and dried and then aged in an oven at 40 ° C. for 48 hours to crosslink to prepare a film sheet.

Using each of the film sheet samples obtained as described above, a test was carried out on substrate adhesion, solvent resistance, presence or absence of deformation of the worksheet, pencil hardness, stain resistance, and abrasion resistance. . Table 5 shows the evaluation results. The test method is as follows. [Adhesion] The base layer of the coating layer was subjected to Cellotape (registered trademark) peeling test. [Solvent resistance] A solvent rubbing test (MEK, ethyl acetate (EAc)) was performed. [Presence or absence of deformation of the worksheet] Place the processed film on a flat place, visually check for curling phenomenon,
The results are shown by the following indices. ：: When there is no curling phenomenon Δ: When there is some curling phenomenon X: When the curling phenomenon is severe.

[Pencil hardness] The pencil hardness was measured using a pencil scratching tester (manufactured by HONJI FUJI) according to the general paint (JIS K5400). [Stain resistance] Magic Ink (registered trademark) (black, red) was applied to the hard coat surface, and after 24 hours, it was wiped off with a dry cloth, and the degree of contamination of the magic ink was visually evaluated. The evaluation results are shown by the following indices. ：: When all of them fell △: When slight contamination was confirmed ×: When severe contamination was found [Abrasion resistance test] Wear wheel H2 using a Taber abrasion machine
2. After the test was performed 200 times under the condition of a load of 500 g, the abrasion state was visually observed, and the results are shown by the following indices. ：: No change in appearance △: Slight wear ×: Very wear

[0042]

[0043] (Note) D-1: 100 parts of a polyisocyanate having an HMDI-based isocyanurate ring (NCO% = 25%), 50 ppm of hydroquinone and 397 parts of ethyl acetate are charged into a container, heated with stirring, and when heated to 60 ° C., 70 parts of 2-hydroxyethyl acrylate was gradually added to 70 parts.
The curing agent was prepared by raising the temperature to ℃ and reacting for 4 hours to confirm that there was no residual NCO by IR. D-2: HMDI trimer (burette bond), NCO%
= 24%.

[0044]

[0045]

As described above, according to the present invention, while being excellent in adhesiveness to various materials, heat resistance, high hardness,
Excellent in cold resistance, abrasion resistance, chemical resistance, weather resistance, stain resistance, lubricity, migration resistance, water repellency, oil repellency, mechanical strength, abrasion resistance, flexibility An ultraviolet curable siloxane-modified polyurethane useful as an ink binder, a coating agent for various sheet materials, and a resist material is provided.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of the polyurethane of Example 3.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazuyuki Hanada 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (72) Inventor Ken Kawaguchi 1-7 Nihonbashi Bakurocho, Chuo-ku, Tokyo No. 6 Inside Dainichi Seika Kogyo Co., Ltd. (72) Inventor Etsuhiro Awaji 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo F-Term inside Dainichi Seika Kogyo Co., Ltd. 4J027 AG03 AG04 AG05 AG06 AG08 AG09 AG13 AG14 AG15 AG23 AG24 AG25 AG27 AG28 BA07 BA08 BA10 BA13 BA19 BA23 BA26 BA27 CB10 CD08 4J034 CA01 CA03 CA04 CA05 CA14 CA15 CA16 CA17 CB02 CB04 CB05 CB07 CB08 CC03 CC08 CC12 CC26 CC34 CC45 CC52 CC61 CC62 CC65 CC11 CD01 DA01 DA03 DA01 DA03 DF12 DF16 DF17 DF20 DF21 DF22 DF32 DG02 DG03 DG04 DG06 DG08 DG09 DG22 DG23 DH02 DM01 DM06 DM09 DM12 DM13 DP12 DP18 DP19 HA01 HA07 H A08 HB15 HC03 HC08 HC09 HC12 HC13 HC22 HC34 HC35 HC46 HC52 HC61 HC64 HC65 HC67 HC68 HC69 HC70 HC71 HC73 RA07

Claims (4)

[Claims] 1. A molecule obtained by reacting a polysiloxane compound having an unsaturated group represented by the following general formula (1) and an active hydrogen-containing group, a polyisocyanate, a polyol or a polyamine, and a chain extender. Has a polysiloxane segment content of 1 to 75% by weight and a weight average molecular weight of 5,000.
UV-curable siloxane-modified polyurethane having a molecular weight of up to 500,000. (However, R in the formula represents a methyl group or a phenyl group, and R ₁
Represents nothing or a divalent organic group, R ₂ represents a hydrogen atom or a hydrocarbon group, X represents an active hydrogen-containing group, and m and n each represent an integer of 1 to 300. ) 2. The ultraviolet-curable siloxane-modified polyurethane according to claim 1, wherein the content of the unsaturated group in the polyurethane molecule is 0.001 to 10 meq / g (polymer). 3. A polysiloxane compound, polyisocyanate, polyol or polyamine having at least one unsaturated group in a side chain and at least one active hydrogen-containing group in a molecular chain terminal and / or a side chain, and chain extension. A method for producing an ultraviolet-curable siloxane-modified polyurethane, comprising reacting an agent. 4. The method for producing an ultraviolet-curable siloxane-modified polyurethane according to claim 3, wherein the polysiloxane compound is a compound represented by the general formula (1).