JPH09324054A - Polyorganosiloxane-modified polymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polygranosiloxane-modified polymer which is excellent in compativility with solvents or high-molecular materials by subjecting a specific monomer to free-radical polymn. in the presence of a mercapto-group-contg. polyorganosiloxane. SOLUTION: A mixture in an amount of 100 pts.wt. consisting of 5-100wt.% monomer (A) having at least one free-radical-polymerizable unsatd. group and at least one sterically hindered piperidyl group with a necessary amt. of a free-radical polymerizable unsatd. monomer (B) is subjected to free-radical polymn. in the presence of 0.1-150 pts.wt. mercapto-group contg. polyorganpsiloxane (C) having a number-average mol.wt. of 50-50,000 at 50-180 deg.C for 1-24hr to give a polyorganosiloxane-modified polymer which comprises (co)polymer units derived from components A and C and polyprganosiloxane units bonded thereto through S atoms and has a number-average mol.wt of 1,000-100,000.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel block or graft polymer having a polyorganosiloxane unit, a method for producing the same, and its use.

[0002]

2. Description of the Related Art As a stabilizer for polymer materials such as plastics, rubbers, fibers, paints and inks, sterically hindered piperidyl group-containing light stabilizers (generally known as hindered amine light stabilizers (HALS)) are Widely used. HALS is considered to suppress the deterioration of polymer materials due to autoxidation, and therefore, it is necessary that HALS be present at the interface with air (oxygen). Therefore, HALS has high mobility and diffusibility in the material. At the same time, it is required that the effect of the added HALS is sufficiently exerted and that the residual rate in the polymer material is high and that the effect does not easily volatilize and the effect lasts for a long time. Various measures have been conventionally attempted to satisfy these conflicting performances.

The use of HALS, which has a relatively high molecular weight and low mobility, is effective in improving the residual rate in the polymeric material, but the stabilizing effect is insufficient with a small amount of addition, and the appearance with a large amount of addition. The physical properties of the base polymer material (plastic, rubber, fiber, paint, ink, etc.) such as mechanical properties are often impaired. Further, when the compatibility between the additive and the base polymer material is insufficient, a phenomenon (bleed phenomenon) in which the additive is deposited on the surface occurs. On the contrary, the use of HALS having a relatively low molecular weight and high mobility has its effect from the beginning, but has a problem that the residual rate in the polymer material is low. JP-A-1-299850 discloses the combined use of a relatively high molecular weight HALS and a relatively low molecular weight HALS as a stabilized polyolefin composition. However, in the above invention, it is an essential component that a benzoate compound and a phosphorus compound are further used in combination,
It is said that it is impossible to obtain a predetermined effect without any of the above.

JP-A-1-261409 discloses an acrylic polyol in which a radically polymerizable HALS monomer and a radically polymerizable ultraviolet absorber are incorporated by copolymerization. However, although this method is effective in improving the residual ratio and compatibility in the polymer material, the stabilizing effect is higher in the HALS monomer. In addition, JP-A-4
JP-A-305584 describes a piperidine-triazine compound having a silane group (a dialkoxysilane having a sterically hindered piperidine structure, a polyorganosiloxane having HALS introduced into a side chain). JP-A-7-2
No. 16754 discloses HA as a non-yellowing woven fabric softening method using a composition containing a polyorganosiloxane.
Polyorganosiloxanes with LS introduced in the side chain are described. However, this method is likely to cause a problem in compatibility with a polymer material, and a problem such as a bleeding phenomenon of an additive or a decrease in transparency in the case of a transparent material is likely to occur.
It is also disadvantageous in terms of cost. A method is known in which a reactive group is introduced onto polypropylene (PP) by graft copolymerization on the surface of a base polymer material, and HALS is introduced on the surface using the reactive group (Ekman, K .; Ek
holm, L.H. Naesman, J .; H. ; JPol
ym Sci Part A, 1995, 33, 269
9). This is expected to achieve both a high residual rate and a high stabilizing effect due to improved volatility and extractability, but there are problems such as the complexity of processing the material later, poor versatility, and cost. It is disadvantageous to see. Therefore, no material has been found that practically sufficiently satisfies the contradictory performance of concentrating at the interface with air with a small amount of addition to exert a stabilizing effect, having high compatibility, and not easily volatilizing.

[0005]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and has a high degree of freedom in designing the structural skeleton of the additive, and is compatible with solvents and various polymer materials. It has excellent solubility and can be concentrated on the surface of polymer materials with a small amount of addition. At the same time, it is excellent in water resistance, water repellency, chemical resistance, low friction, etc. of polyorganosiloxane. Suitable as a photostabilizer for polymeric materials that can impart the above properties economically and easily (a)
A (co) polymer unit derived from a radical-polymerizable HALS monomer (or that monomer and another radical-polymerizable monomer) and (b) a polyorganosiloxane unit are bonded via a sulfur atom. An object of the present invention is to provide a block or graft polymer characterized by the above. Another object of the present invention relates to a method for producing the above polyorganosiloxane-modified polymer, which can be obtained by a simple synthetic method and has a low production cost and excellent economy.

[0006]

Means for Solving the Problems In order to solve the problems associated with the prior art, the present inventors have conducted intensive studies, and as a result,
The present invention has been made. That is, the (co) polymer unit and the (b) polyorganosiloxane unit derived from the (a) radical-polymerizable HALS monomer (or the monomer and another radical-polymerizable monomer) according to the present invention are The block or graft polymer characterized by being bonded via a sulfur atom can be suitably used as a light stabilizer for a polymer material. The polyorganosiloxane-modified polymer is introduced as polysilsesquioxane and / or polydialkylsiloxane as a polyorganosiloxane unit, and (1) a radically polymerizable HALS monomer is added in the presence of a mercapto group-containing polyorganosiloxane. A polyorganosiloxane-modified resin obtained by polymerization in. (2) A polyorganosiloxane-modified polymer obtained by polymerizing a radically polymerizable HALS monomer and a radically polymerizable unsaturated monomer in the presence of a mercapto group-containing polyorganosiloxane. The present invention also relates to a method for producing the polyorganosiloxane-modified polymer described above.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The polyorganosiloxane-modified polymer according to the present invention will be specifically described below. The polyorganosiloxane-modified polymer includes (a) a (co) polymer unit derived from a radically polymerizable HALS monomer (or the monomer and another radically polymerizable monomer) and (b) a polyorganosiloxane unit. Is a block or graft polymer characterized by being bonded via a sulfur atom, and preferably (i) one or two of the substituents (side chain and main chain end) of the polyorganosiloxane. The above is the following formula (I), and in the other substituent, the side chain substituent is a group selected from an alkyl group, an aralkyl group, and a substituted or unsubstituted phenyl group, and the main chain terminal group is a trialkylsilyl group. (Ii) A block or graft polymer having a number average molecular weight of 1,000 to 100,000.

—R ¹ —X ¹ —R ² —S—R ³ (I) [In the formula (I), R ¹ may have a substituent, and includes O and S which are heteroatoms. May be an alkylene group (eg, —C ₃ H ₆ —S—CH ₂ CH (CH ₃ ) —), and X ¹ is a single bond, an ester bond, a sulfide bond, an amide bond, a urethane bond, a urea bond, or thiourethane. Represents a bond, an ether bond or a carbonyl bond, R ² represents an alkylene group which may have a substituent and may contain O, S or N of a hetero atom or a single bond, and polyorgano siloxane and -R ¹ -X ¹ -R ²
Up to the -group represents a polyorganosiloxane unit.
R ³ is the following formula (II) -1 or formula (II) -1 and (II)
Shows a (co) polymer unit consisting of a repeating unit represented by -2. Here, when it is derived from a radically polymerizable HALS monomer, it is represented by formula (II) -1, and when it is derived from a radically polymerizable HALS monomer and another radically polymerizable monomer, it is represented by formula (II) -1. And (II) -2 are represented by the repeating unit.

[0009]

Embedded image In formula (II) -1, R ⁴ represents a hydrogen atom or a carbon number of 1 to 3.
Represents an alkyl group of, Y ¹ represents a single bond, a substituted or unsubstituted phenylene group and a group represented by the following structure,

Embedded image Alternatively, these groups represent the same or different plural groups bonded to each other, wherein R ¹⁵ represents an alkylene group having 1 to 22 carbon atoms (exemplified below), a phenylene group or a plurality of these groups bonded to each other. Is shown.

Embedded image

R ⁵ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, R ⁶
R ⁷ , R ⁸ and R ⁹ each independently represent an alkyl group which may have a branched structure having 1 to 5 carbon atoms. R ¹⁰ represents a hydrogen atom or a cyano group. This structure shows various structures depending on the combination of the defined groups (R, X, Y) showing the structure derived from the radically polymerizable HALS monomer, and is not particularly limited as long as it follows the definition, but in organic chemistry It does not include structures that are theoretically impossible. To illustrate the structure according to the above definition

[Chemical 6] Etc. In formula (II) -2, R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Y ¹ , Y ² and Y ³ are defined for R ^4. And Y ² and Y ³ are the same as those described above.
Same as defined for ¹ .

Alternatively, the same or different plural groups of these groups are bonded to each other, wherein R ¹³ and R ¹⁴ are each independently a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms, a phenoxy group, an amino group, Or an alkyl group which may be substituted with these groups and which may have a branched structure having 1 to 22 carbon atoms (exemplified below), (hydroxyl group)

[Chemical 7] (Alkoxy group having 1 to 5 carbon atoms)

Embedded image (Phenoxy group)

Embedded image (Amino group)

Embedded image A substituted or unsubstituted ring structure group containing a hydrogen atom, a methyl group, and O, S, N as a hetero atom (representing an aromatic ring, an alicyclic ring, and a hetero ring containing O, S, N as a hetero atom) (exemplified below. ),

[0012]

Embedded image A polyorganosiloxane having a side chain composed of one or more groups selected from an alkyl group, an aralkyl group, a substituted or unsubstituted phenyl group, and a main chain terminal group composed of a trialkylsilyl group (shown below) Example).

[Chemical 12] Formula (II) -2 also has various structures depending on the combination of the defined groups (R, X, Y) and is not particularly limited as long as it follows the definition, but does not include a structure theoretically impossible in organic chemistry. The structure according to the above definition is exemplified below. ]

(R ¹⁴ is a hydroxyl group or an alkyl group substituted with a hydroxyl group)

Embedded image (R ¹⁴ is an alkoxy group or an alkyl group substituted with an alkoxy group)

Embedded image (R ¹⁴ is a phenoxy group)

Embedded image (R ¹⁴ is an amino group)

Embedded image (R ¹³ is a hydrogen atom or a methyl group, and R ¹⁴ is a methyl group)

Embedded image (R ¹⁴ is a substituted or unsubstituted ring structure group containing O, S, N as a hetero atom)

Embedded image (R ¹⁴ is a polyorganosiloxane in which the side chain is one or two or more groups selected from an alkyl group, an aralkyl group, a substituted or unsubstituted phenyl group, and the main chain terminal group is a trialkylsilyl group)

Embedded image

The polyorganosiloxane-modified polymer according to the present invention comprises (1) radical (co) polymerization of at least one radically polymerizable HALS monomer. (2) Radical copolymerization of at least one radical-polymerizable HALS monomer and at least one radical-polymerizable unsaturated monomer. The reaction for obtaining the (co) polymer unit derived from the radically polymerizable HALS monomer is carried out in the coexistence of polysilsesquioxane and / or polydialkylsiloxane containing at least one mercapto group in one molecule. Is obtained by The polyorganosiloxane-modified polymer is considered to have the following structure. That is, when one mercapto group is present in the polyorganosiloxane, the polyorganosiloxane unit is radically polymerizable HA.
It becomes a block copolymer added to one end of the (co) polymer unit derived from the LS monomer. When two mercapto groups are present on both ends of the polyorganosiloxane, the polyorganosiloxane unit contains radically polymerizable HA.
It becomes a block copolymer in which (co) polymer units derived from the LS monomer are added to both ends. When three or more mercapto groups are present in the molecule of the polyorganosiloxane, the polyorganosiloxane unit is radically polymerizable H
It becomes a graft copolymer in which a plurality of (co) polymer units derived from ALS monomers are added, and the so-called comb-shaped copolymer (for example, as a polyorganosiloxane can be comparatively used as a polyorganosiloxane, depending on the molecular weight of the polyorganosiloxane and the content of the mercapto group). It has a high molecular weight and a high mercapto group content, or a star-type copolymer (for example, a polyorganosiloxane having a relatively low molecular weight and a high mercapto group content is used).

In the above polyorganosiloxane-modified polymer, when a polysilsesquioxane having at least one mercapto group in the molecule and a polydialkylsiloxane are used together when the polyorganosiloxane unit is introduced, the polyorganosiloxane-modified resin is a polysiloxane. It is obtained as a mixture of a block / graft copolymer having a lusesquioxane unit and one having a polydialkylsiloxane unit. As the radically polymerizable HALS monomer,
There is no particular limitation as long as it is a monomer having at least one radically polymerizable unsaturated group and at least one sterically hindered piperidyl group in the molecule. For example, 1, 2, 2,
6,6-Pentamethyl-4-piperidyl (meth) acrylate, 2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, 1,2,2,6,6-pentamethyl-4-piperidyl (meth) ) Acrylamide, 2,
2,6,6-Tetramethyl-4-piperidyl (meth) acrylamide, 1,2,2,6,6-pentamethyl-4
-Cyano-4-piperidyl (meth) acrylamide,
Examples thereof include (meth) acrylates such as 2,2,6,6-tetramethyl-4-cyano-4-piperidyl (meth) acrylamide, and (meth) acrylamides. Of these, considering the availability, 1, 2, 2,
6,6-Pentamethyl-4-piperidyl (meth) acrylate and 2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate are preferred. In addition, these monomers can be freely selected and used within a range that does not cause a problem such as gelation during polymerization in consideration of intended physical properties of the polyorganosiloxane-modified polymer. The monomers can be used alone or in combination of two or more kinds.

The amount used is required to be compatible with the base polymer material (plastic, rubber, fiber, paint, ink, etc.) to which the polyorganosiloxane-modified polymer according to the present invention is added and the light stabilizing ability. It is not particularly limited as long as it satisfies the following performance, but it can be selected in the raw material monomer (5 to 100% by weight, preferably 15 to 100% by weight. The polyorganosiloxane-modified polymer of the present invention can be selected. As the radical-polymerizable unsaturated monomer used in the synthesis, generally, any radical-polymerizable unsaturated monomer can be used.

For example, alkyl (carbon number 1) such as methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and stearyl (meth) acrylate.
-22) (meth) acrylates. Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate (eg, Nippon Kayaku Co., Ltd.) glycidyl (meth) acrylate And a (meth) acrylate of a substituted or unsubstituted phenyl group-containing organic group. Alkyl ether (meth) acrylates such as 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and n-butoxyethyl (meth) acrylate; Phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol acrylate (eg, Biscoat # 150 of Osaka Organic Chemical Industry Co., Ltd.), ring structure containing heteroatoms or substituted or unsubstituted phenyl group-containing organic group ether (meth) Acrylate.

Polyethylene glycol monomethacrylate (Example: Bremmer PE series manufactured by NOF Corporation, PE-9)
0, PE-200, PE-350), methoxy polyethylene glycol monomethacrylate (Example: Bremmer PME series manufactured by NOF CORPORATION, PME-100, PME-200, PME-400), polypropylene glycol monomethacrylate (Example: Japan Oil & Fat Co., Ltd. Bremmer PP series, PP-1000, PP-50
0, PP-800), polyethylene glycol polypropylene glycol monomethacrylate (eg, Blemmer PEP series, 70PEP-370B, manufactured by NOF Corporation), polyethylene glycol polytetramethylene glycol monomethacrylate (eg, Blemmer 55PET, manufactured by NOF Corporation) -800
), Polypropylene glycol polytetramethylene glycol monomethacrylate (Example: Bremmer NKH-5050 manufactured by NOF Corporation), polypropylene glycol monoacrylate (Example: Bremmer AP-40 manufactured by NOF Corporation)
0), polyethylene glycol monoacrylate (eg:
Nippon Oil & Fat Co., Ltd.'s Bremmer AE-350), ethoxydiethylene glycol (meth) acrylate, etc. alkoxypolyethylene glycol or alkoxypolypropylene glycol (meth) acrylate, light acrylate NP-8EA, NP-4EA (both former two are Kyoeisha Chemical (Manufactured by Co., Ltd.), a (meth) acrylate of an alkoxypolyethylene glycol or an alkoxypolypropylene glycol having a ring structure or a hetero atom (excluding an epoxy group-containing organic group) and a ring structure or a substituted or unsubstituted phenyl group. Also included are monomers having a plurality of radically polymerizable groups such as allyl (meth) acrylate, triethylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate. This includes urethane (meth) acrylates (eg, Kyoeisha Chemical Co., Ltd., urethane acrylate series, AH-600, AI-60).
0, AT-600), methacryl group-modified polyorganosiloxane (eg: Shin-Etsu Chemical Co., Ltd., X-22-16)
4B, X-22-164C, X-22-174DX) and other polymers and oligomers having relatively high molecular weight.

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2
-Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and other C2-10 hydroxyalkyl acrylates, 2-hydroxy-3-
Phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, 2- (meth) acryloyloxyethyl-
2-hydroxypropyl phthalate, 3-chloro-2-
(Meth) such as hydroxypropyl (meth) acrylate
Also included are acrylates and (meth) acrylates having multiple hydroxyl groups in one molecule such as glycerol mono (meth) acrylate. Lactone-modified (meth) acrylates obtained by adding 1 to 5 mol of lactones such as ε-caprolactone and δ-caprolactone to these hydroxyl group-containing (meth) acrylates are also exemplified. Examples of this lactone-modified (meth) acrylate include the following PLAXEL FA series and PLAXEL FM series (both manufactured by Daicel Chemical Industries Ltd.): PLAXEL FA-
1 (monomer of 1 mol of 2-hydroxyethyl acrylate and 1 mol of ε-caprolactone), Praxel F
A-4 (2-hydroxyethyl acrylate 1 mol ε
-Monomer added with 4 mol of caprolactone), Praxel FM-1 (monomer added with 1 mol of ε-caprolactone to 1 mol of 2-hydroxyethyl acrylate), Praxel FM-3 (1 mol of 2-hydroxyethyl methacrylate) A monomer obtained by adding 3 mol of ε-caprolactone) to Praxel FM-4 (a monomer obtained by adding 4 mol of ε-caprolactone to 1 mol of 2-hydroxyethyl methacrylate).

Also included are monomers having a plurality of radically polymerizable groups such as glycerol di (meth) acrylate.
This includes epoxy (meth) acrylate (eg, manufactured by Kyoeisha Chemical Co., Ltd., epoxy ester series 40EM, 70
PA, 3000M etc.), and macromonomers having relatively high molecular weights such as polymers and oligomers.
(Meth) acrylonitrile, (meth) acrylamide,
Amide compounds of (meth) acrylates such as N, N-dimethylacrylamide, N-isopropylacrylamide, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylate, N- (meth) acrylmorpholine and their derivatives are Can be mentioned. Styrene, α-methylstyrene, p-methylstyrene, aromatic vinyl compounds such as vinyltoluene, vinylcyclohexane, 2-vinylpyridine, 4-vinylpyridine, N-vinylpyrrolidone, N-
Vinyl compounds having a ring structure such as vinyl-2-piperidone and vinyloxazoline or a ring structure group containing a hetero atom (excluding an epoxy group-containing organic group). Maleimide derivatives such as N-phenylmaleimide, N- (2-methylphenyl) maleimide and N-cyclohexylmaleimide Maleic acid esters such as diethyl maleate and di-2-ethylhexyl maleate. Fumaric acid esters such as diethyl fumarate and di-2-ethylhexyl fumarate; Aliphatic vinyl compounds such as vinyl chloride, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinylformamide and derivatives thereof. Aliphatic vinyl esters such as vinyl acetate and vinyl propionate.

Such a radical-polymerizable unsaturated monomer can be freely selected and used within a range that does not cause a problem such as gelation during polymerization in consideration of the desired physical properties of the polyorganosiloxane-modified resin, At this time, these monomers can be used alone or in combination of two or more kinds. Considering the simplicity of polymerization and the variety of polymer properties, (meth) acrylates are preferred for use as the main component in view of their abundance. At this time, in consideration of cost, it is preferable to use a general-purpose monomer such as methyl methacrylate, styrene, or vinyl acetate together. Further, when a monomer having a plurality of radically polymerizable groups is used, it becomes a cross-linking point, so the amount used to prevent gelation during polymerization is approximately the methacrylic group content in the monomer or the mercapto group-containing polyamine. 0.05 to 5% by weight, depending on the content and amount of mercapto group in the organosiloxane
Is preferred.

Examples of the mercapto group-containing polyorganosiloxane compound in the present invention include polysilsesquioxane or polydialkylsiloxane having a main chain skeleton. When the main chain skeleton is polysilsesquioxane, there are a mercapto group introduced into the side chain (a) and a mercapto group introduced into the end of the main chain (b). Polysilsesquioxane (a) having a mercapto group introduced into its side chain
Has, for example, a structure represented by the following formula (A):

Embedded image In the formula, -R ^m and -R ⁿ are side chain organic groups, and -OR ^q and -R
OR ^r , —OR ^s , and —OR ^t are terminal groups of the main chain, and p
Is a repeating unit. Main chain end group (in formula (A),
^{OR q, -OR r, -OR s} , -OR t) is trialkyl silylating, trialkylsilyl group (-O-
SiR ¹ R ² R ³ : R ¹ , R ² and R ³ represent the same or different alkyl groups).

Further, a side chain organic group (in the formula (A), --R
^m , —R ⁿ ) is composed of only a mercapto group-containing organic group represented by the following formula [1], or is selected from an alkyl group, an aralkyl group and a substituted or unsubstituted phenyl group. Both of them may exist. Such a mercapto group-containing organic group [1] is, in the mercaptan group-containing polysilsesquioxane, usually 5.0 or less, and preferably 3 or less, on average per molecule of all side chain organic groups. .2, more preferably 1.6
Less than or equal to is desirable. -R ⁴ -SH ......... [1] (wherein [1], R ⁴ represents C 1-20 alkyl group carbon atoms, an alkenyl group, an aralkyl group, a substituted or unsubstituted phenyl group) the mercapto group-containing Porishiru The number average molecular weight of the sesquioxane (a) is not particularly limited, but is preferably 500 to
50,000, particularly preferably 1000 to 1000
0. The method for producing the polysilsesquioxane (a) in which a mercapto group is introduced into the side chain is not particularly limited, but as an example, it can be produced by the method described in Japanese Patent Application No. 7-337571 by the applicant. it can.

The polysilsesquioxane (b) having a mercapto group introduced at the end of the main chain has a structure represented by the following formula (B),

[Chemical 21] In the formula, -R ^m and -R ⁿ are side chain organic groups, and -OR ^u and -R
OR ^v , -OR ^w , -OR ^y are terminal groups of the main chain, and p
Is a repeating unit. In the mercapto group-containing polysilsesquioxane according to the present invention, the main chain terminal group (in the formula (B), —OR ^u , —OR ^v , —OR ^w , and —OR ^y ) is trialkylsilylated or main chain terminal. At least one of the groups is a trialkylsilyloxy group containing a mercapto group per molecule. The terminal trialkylsilyloxy group containing no mercapto group is -O-SiR ¹ R ²
R ³ (R ¹ , R ² and R ³ represent the same or different alkyl groups from each other), and the trialkylsilyloxy group containing a mercapto group is represented by —O—Si (R ¹ ) (R
² ) R ⁴ SH (R ⁴ represents an alkyl group, an aralkyl group, or a substituted or unsubstituted phenyl group).

The mercapto group in the main chain terminal group is not particularly limited, but in the polysilsesquioxane, of all main chain terminal groups, preferably 1.0 or more on average per molecule. 4.0 or less, particularly preferably 1.0 or more and 3.5 or less, further preferably 1.0 or more 2.
0 or less is desirable. The number average molecular weight of the mercapto group-containing polysilsesquioxane (b) is not particularly limited, but is preferably 500 to 50,000, and particularly preferably 1,000 to 10,000. The polysilsesquioxane (b) having a mercapto group introduced at the end of the main chain can be produced by a method similar to that of the polysilsesquioxane (a) having a mercapto group introduced at the side chain. The amount of water for hydrolytic condensation during production, the type of catalyst, the amount of catalyst, and the reaction temperature can be determined by the applicant of the present application in Japanese Patent Application No. 7-33757.
Similar to the method described in No. 1. In the case of producing a polysilsesquioxane (b) having a mercapto group introduced at the end of the main chain, the difference from the polysilsesquioxane (a) having a mercapto group introduced at the side chain will be described. The trialkoxysilane and / or trichlorosilane that can be used in the production of the polysilsesquioxane (b) in which a mercapto group is introduced at the end of the main chain is an alkyl group, an alkenyl group, an aralkyl group, a substituted or non-substituted one. It is a trialkoxysilane and / or a trichlorosilane having a substituted phenyl group, and it is not necessary to use a trialkoxysilane and / or a trichlorosilane having a mercapto group. Further, the silylating agent that can be used in the production of the polysilsesquioxane (b) having a mercapto group introduced at the terminal of the main chain is only the silylating agent having a mercapto group, Both of those described in JP-A 7-337571, and the respective proportions may be adjusted according to the amount of mercaptan to be introduced. Examples of the silylating agent having a mercapto group include 1,3-bis (3-mercaptopropyl) tetramethyldisiloxane, dimethylmercaptopropylmethoxysilane, and dimethylmercaptopropylchlorosilane.

When the main chain skeleton is a polydialkylsiloxane, the polydialkylsiloxane containing at least one mercapto group is a polydialkylsiloxane having a mercapto group introduced into its side chain (side chain type) or a polydialkylsiloxane. One with a mercapto group introduced at both ends (both ends), one with a mercapto group introduced at one end of polydialkylsiloxane (one end), and one having a mercapto group at both the side chain and both ends of polydialkylsiloxane Some (side chain both ends type). If you show a representative example,

Embedded image And the like. The number of mercapto groups in the polydialkylsiloxane containing a mercapto group is usually 1.0 or more and 5.0 or less, preferably 1.0 or more and 3.5 or less per molecule in the polydialkylsiloxane. , And more preferably 1.0 or more and 2.0 or less.

The number average molecular weight of the mercapto group-containing polydialkylsiloxane according to the present invention is not particularly limited, but is preferably 500 to 50,000, and particularly preferably 1,000 to 10,000. About the mercapto group-containing polydialkylsiloxane, as long as it has the above structure, regardless of the production method, a generally known production method of a mercapto-modified polydialkylsiloxane, for example, hydrolysis of mercaptopropylmethyldimethoxysilane. A method for producing a side chain-type modified polydialkylsiloxane by using the siloxane oligomer and cyclic siloxane obtained by the above, and an acidic catalyst. In addition, a production method of obtaining a modified polydialkylsiloxane having both ends at the ends by using bis (mercaptopropyl) tetramethyldisiloxane, a cyclic siloxane, and an acidic catalyst can be mentioned. In addition, a mercapto-modified polydialkylsiloxane that is generally commercially available as an approximately mercapto group-containing polydialkylsiloxane may be used, for example, X-22- manufactured by Shin-Etsu Chemical Co., Ltd.
167B (mercapto modified type at both ends), KF-200
1, KF-2002 (side chain mercapto modified type) and the like. The amount of the above-mentioned polyorganosiloxane compound containing one or more mercapto groups is the amount of the other monomer to be usually reacted (radical polymerizable HALS monomer alone or in combination with radical polymerizable unsaturated monomer). It may be selected in the range of 0.1 to 150 parts by weight, preferably 0.1 to 60 parts by weight, relative to 100 parts by weight).

The polyorganosiloxane-modified polymer according to the present invention can be synthesized according to the following procedure. That is, the radically polymerizable HALS monomer is
Add a radically polymerizable unsaturated monomer if necessary,
A polyorganosiloxane compound containing one or more mercapto groups in a predetermined ratio is mixed and polymerized in the presence of a radical polymerization initiator. The polymerization can be carried out by a conventionally known radical polymerization method. The above radical polymerization initiator can be used as long as it is used as a general radical polymerization reaction initiator, for example, 2,2′-azobis (isobutylnitrile), 2,2′-azobis (2,2
4-dimethyl-4-methoxyvaleronitrile), 2-cyano-2-propylazo-formamide, dimethyl 2,2′-azobis (2-methylpropionate),
2,2'-azobis (2-hydroxymethylpropionitrile), 2,2'-azobis {2-methyl-N- (2
-Hydroxyethyl) -propionamide} and other azo-based polymerization initiators such as isobutyl peroxide, 2,
Examples include peroxide-based polymerization initiators such as 4-dichlorobenzoyl peroxide, benzoyl peroxide, t-butyl peroxide, t-butyl cumyl peroxide, and t-butyl hydroperoxide.
These can be used alone or in combination of two or more. At this time, the same or different polymerization initiators may be additionally added during the reaction for the purpose of reducing the concentration of the reaction residue. However, the use of a peroxide-based polymerization initiator, as a radically polymerizable unsaturated monomer
When N-vinylpyrrolidone or the like is used, it is preferable to use an azo-based polymerization initiator because there are improper combinations such as redox reaction is prioritized over polymerization.

The reaction can be carried out at normal pressure. The reaction temperature is not particularly limited as long as it is a temperature at which the radical polymerization reaction initiator is decomposed, and it is usually preferably in the range of 50 to + 180 ° C., and a method of gradually increasing from low temperature to high temperature may be employed. If the reaction temperature is lower than 50 ° C., the reaction takes a long time, and if it exceeds + 180 ° C., the pressure during the reaction becomes high and the reaction operation becomes difficult, which is not preferable. The reaction time is not particularly limited, but usually 1 to
It can be performed within a range of 24 hours, and industrially 3 to 10
It is desirable to set the time range. In the production method of the present invention, the polyorganosiloxane-modified light stabilizer of interest can be obtained by a one-step reaction under the various reaction conditions described above, but it is usually an organic solvent for handling the polymerization reaction operation and carrying out the reaction more smoothly. It is preferably carried out in the presence of a solvent. The organic solvent is appropriately selected from conventionally known ones that are substantially inactive with respect to the raw material monomers and organosiloxanes during the polymerization reaction and can dissolve or disperse these raw materials. Can be used. For example, aromatic hydrocarbons such as benzene, toluene and xylene. Aliphatic hydrocarbons such as n-hexane and cyclohexane. Esters such as ethyl acetate, butyl acetate and amyl acetate. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Alcohols such as methanol, ethanol, isopropanol, butanol, 1,2,6-hexanetriol and glycerin. Ethers such as tetrahydrofuran and 1,4-dioxane.
Amides such as n, n-dimethylformamide, n-methylformamide, n, n-diethylformamide, n-methylacetamide, n, n-dimethylacetamide, and n-methylpropionamide. Pyrrolidones such as 1-methyl-2-pyrrolidone, 2-pyrrolidone and ε-caprolactam. Ethylene glycol, propylene glycol,
Glycols such as butylene glycol, trimethylene glycol, triethylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol. 2-methoxyethanol,
2-ethoxyethanol, 2- (methoxymethoxy) ethanol, 2-propoxyethanol, 2-butoxyethanol, diethylene glycol monomethyl ether,
Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether And glycol ethers such as 3-methoxy-3-methyl-1-butanol.

These solvents may be used as a mixture of two or more kinds. Further, the mixing ratio of the organic solvent is not particularly limited, and an appropriate ratio may be selected depending on the viscosity and solubility of the resulting polyorganosiloxane-modified light stabilizer and raw materials. Usually about 1 to 80% by weight,
From the viewpoint of operability of reaction and easiness of handling of product purification (if necessary), 5 to 40% by weight is desirable. The polyorganosiloxane-modified light stabilizer thus obtained may have a number average molecular weight of 1,000 to 100,000, preferably 3,000 to 50,000. When the number average molecular weight is less than 1000, it is difficult to substantially have the structure of the polyorganosiloxane-modified light stabilizer according to the present invention, and when the number average molecular weight is more than 100,000, the compatibility with other polymer materials is low. It is not preferable because it tends to decrease and bleeding phenomenon and the physical properties of the base polymer material are impaired. The reaction product obtained by the production method of the present invention,
Depending on the purpose of use, it may be used as it is as a light stabilizer. Further, it can be purified by a known method such as column chromatography, reprecipitation and dialysis.

[0031]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 Synthesis of mercapto group-containing polysilsesquioxane: Polymer A 3-mercaptopropyltrimethoxysilane 9.98 was placed in a 500 cc flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. g (50.87 mmol), methyltriethoxysilane 199.55 g (1119.13 mmol), phenyltrimethoxysilane 5.95 g (30.00 mmol) and pure water 64.87 g
(3600.00 mmol) was charged, and the temperature of the solution was kept at 5 ° C. with stirring under a nitrogen stream. While stirring, 12.15 g of 3.6% hydrochloric acid aqueous solution was added dropwise over 30 minutes, and the solution temperature was kept at 10 ° C for 1 hour. Then raise the temperature of the solution to 70 ° C 3
After reacting for 29 hours, 29.16 g of hexaethyldisiloxane (179.60 mmol) was added, and stirring was continued at 70 ° C. for 3 hours. The solution temperature was lowered to 40 ° C., and 13.47 g of a 4.3 wt% methanol solution of potassium hydroxide was added, and the mixture was stirred at room temperature for 2 hours and left standing for 12 hours. Remove the lower layer and add 150 g of butyl acetate, then add 40
After concentrating at 200 ° C. under reduced pressure of 200 mmHg and distilling off 150 g of liquid, 200 g of butyl acetate was further added at normal pressure, and the mixture was stirred for 1 hour. After the obtained solution was filtered, it was further concentrated under reduced pressure to obtain 82.68 g of a colorless, transparent, viscous liquid. The molecular weight of the obtained product was measured by gel permeation chromatography (hereinafter abbreviated as GPC) (in terms of polystyrene), and the result was Mn = 3300 (where Mn is the number average molecular weight). From the IR spectrum and the Raman spectrum, an absorption based on a mercapto group appeared around 2560 cm ^-1 . Let the obtained polymer be the polymer A.

(Example 2) Synthesis of mercapto group-containing polysilsesquioxane: Polymer B 3-mercaptopropyltrimethoxysilane 9.98 in a 500 cc flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. g (50.87 mmol), methyltriethoxysilane 199.55 g (1119.13 mmol), phenyltrimethoxysilane 5.95 g (30.00 mmol) and pure water 64.87 g
(3600.00 mmol) was charged, and the temperature of the solution was kept at 5 ° C. with stirring under a nitrogen stream. While stirring, 12.15 g of 3.6% hydrochloric acid aqueous solution was added dropwise over 30 minutes, and the solution temperature was kept at 10 ° C. for 1 hour. Then raise the temperature of the solution to 70 ° C 3
After reacting for 50 hours, 50.75 g of 1,3-bis (3-mercaptopropyl) tetramethyldisiloxane (179.60
mmol) was added and stirring was continued at 70 ° C. for 3 hours.
The solution temperature was lowered to 40 ° C., and 13.47 g of a 4.3% methanol solution of potassium hydroxide was added, and the mixture was stirred at room temperature for 2 hours and left standing for 12 hours. After removing the lower layer, add 150 g of butyl acetate, concentrate under reduced pressure of 200 mmHg at 40 ° C with stirring, distill off 150 g of liquid, and then add 200 g of butyl acetate at atmospheric pressure. Then, the mixture was stirred for 1 hour. The resulting solution was filtered and then concentrated under reduced pressure to obtain 84.3 g of a colorless transparent viscous liquid. The number average molecular weight of this product was 3,200 as measured by GPC. 256 from IR spectrum and Raman spectrum
Absorption based on the mercapto group appeared near 0 cm ^-1 .
Let the obtained polymer be the polymer B.

(Example 3) 2.50 g (25.0 mm) of methyl methacrylate was placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser.
ol), 2-hydroxyethyl methacrylate 2.
50 g (19.2 mmol), 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate of 5.0
After charging 0 g (21.0 mmol) and 1.00 g of polymer A, 26.0 g of n-butyl acetate containing 0.167 g (0.72 mmol) of dimethyl 2,2-azobis (2-methylpropionate) was added. Then, the temperature was raised with stirring under a nitrogen atmosphere and the temperature was maintained at 80 ° C. for 3 hours, and then dimethyl 2,2-azobis (2-methylpropionate) was further added.
3.0 g of n-butyl acetate containing 0.167 g (0.72 mmol) was added, and the reaction was continued at 90 ° C. for 3 hours. After cooling to room temperature, 40 g of a colorless transparent solution was obtained. This solution is reprecipitated with hexane, and the obtained precipitate is thoroughly washed with hexane. Thereafter, heating and vacuum drying are performed at 40 to 50 ° C. for 24 hours to remove the solvent and the like. The molecular weight of the obtained product was measured by GPC, and the result was Mn = 9200.
As a result of elemental analysis, carbon 59%, oxygen 25%, nitrogen 2.5
%, Silicon 3.4%, and sulfur 0.1%. The absorption due to the mercapto group near 2560 cm ⁻¹ in the Raman spectrum due to polymer A disappeared.

Example 4 1.14 g (11.4 mm) of methyl methacrylate was placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a reflux condenser.
ol), 2-hydroxyethyl methacrylate 2.
95 g (22.7 mmol), 5.9 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate
After charging 1 g (24.8 mmol) and 3.00 g of polymer A, 26.0 g of n-butyl acetate containing 0.105 g (0.45 mmol) of dimethyl 2,2-azobis (2-methylpropionate) was added. Then, the temperature was raised with stirring under a nitrogen atmosphere and the temperature was maintained at 80 ° C. for 3 hours, and then dimethyl 2,2-azobis (2-methylpropionate) was further added.
3.0 g of n-butyl acetate containing 0.167 g (0.72 mmol) was added, and the reaction was continued at 90 ° C. for 3 hours. After cooling to room temperature, 40 g of a colorless transparent solution was obtained. This solution is reprecipitated with hexane, and the obtained precipitate is thoroughly washed with hexane. Thereafter, heating and vacuum drying are performed at 40 to 50 ° C. for 24 hours to remove the solvent and the like. The molecular weight of the obtained product was measured by GPC, and the result was Mn = 7200.
As a result of elemental analysis, carbon 53%, oxygen 26%, nitrogen 2.3
%, Silicon 9.5%, and sulfur 0.2%. The absorption due to the mercapto group near 2560 cm ⁻¹ in the Raman spectrum due to polymer A disappeared.

Example 5 2.24 g (22.4 mm) of methyl methacrylate was placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a reflux condenser.
ol), Blemmer PME-400 (Methoxypolyethylene glycol monomethacrylate manufactured by NOF CORPORATION)
5.43 g (11.2 mmol), 1,2,2,6,6
-Pentamethyl-4-piperidyl methacrylate 2.33 g (9.8 mmol) and polymer A 1.13.
After charging g, 0.082 g (0.36 mmol) of dimethyl 2,2-azobis (2-methylpropionate)
N-Butyl acetate containing 26.0 g was added, the temperature was raised with stirring under a nitrogen atmosphere and the temperature was maintained at 80 ° C. for 3 hours, and then 0.167 g of dimethyl 2,2-azobis (2-methylpropionate) was further added. Acetic acid n- containing (0.72 mmol)
3.0 g of butyl was added and the reaction was continued at 90 ° C. for 3 hours.
After cooling to room temperature, 40 g of a colorless transparent solution was obtained. This solution is reprecipitated with hexane, and the obtained precipitate is thoroughly washed with hexane. Thereafter, heating and vacuum drying are performed at 40 to 50 ° C. for 24 hours to remove the solvent and the like. The molecular weight of the obtained product was measured by GPC, and the result was Mn = 7700. As a result of elemental analysis, carbon was 55%, oxygen was 30%, nitrogen was 1.0%, silicon was 4.1%, and sulfur was 0.1%.
Raman spectrum 2560 cm due to polymer A
^The absorption due to the mercapto group near ^-1 disappeared.

(Example 6) 2.50 g (25.0 mm) of methyl methacrylate was placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser.
ol), 2-hydroxyethyl methacrylate 2.
50 g (19.2 mmol), 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate of 5.0
After charging 0 g (21.0 mmol) and 1.0 g of the polymer B, 26.0 g of n-butyl acetate containing 0.167 g (0.72 mmol) of dimethyl 2,2-azobis (2-methylpropionate) was added. Then, the temperature was raised with stirring under a nitrogen atmosphere and the temperature was maintained at 80 ° C. for 3 hours, and then dimethyl 2,2-azobis (2-methylpropionate) was further added.
3.0 g of n-butyl acetate containing 0.167 g (0.72 mmol) was added, and the reaction was continued at 90 ° C. for 3 hours. After cooling to room temperature, 40 g of a colorless transparent solution was obtained. This solution is reprecipitated with hexane, and the obtained precipitate is thoroughly washed with hexane. Thereafter, heating and vacuum drying are performed at 40 to 50 ° C. for 24 hours to remove the solvent and the like. The molecular weight of the obtained product was measured by GPC, and the result was Mn = 9800.
As a result of elemental analysis, carbon 59%, oxygen 25%, nitrogen 2.3
%, Silicon 3.1%, and sulfur 0.1%. The absorption due to the mercapto group near 2560 cm ⁻¹ in the Raman spectrum due to polymer A disappeared.

(Example 7) 2.50 g (25.0 mm) of methyl methacrylate was placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser.
ol), 2-hydroxyethyl methacrylate 2.
50 g (19.2 mmol), 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate of 5.0
0 g (21.0 mmol) and X-22-167B (manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane having a mercapto group introduced at both ends) were charged, and then dimethyl 2,2-azobis (2- Methyl propionate)
After adding 26.0 g of n-butyl acetate containing 0.167 g (0.72 mmol), the temperature was raised with stirring under a nitrogen atmosphere and the temperature was maintained at 80 ° C. for 3 hours, and then dimethyl 2,2-
Azobis (2-methylpropionate) 0.167g
3.0 g of n-butyl acetate containing (0.72 mmol) was added, and the reaction was continued at 90 ° C. for 3 hours. After cooling to room temperature,
40 g of a colorless transparent solution was obtained. This solution is reprecipitated with hexane, and the obtained precipitate is thoroughly washed with hexane. Thereafter, heating and vacuum drying are performed at 40 to 50 ° C. for 24 hours to remove the solvent and the like. The molecular weight of the obtained product was measured by GPC, and the result was Mn = 11,000. As a result of elemental analysis, carbon was 61%, oxygen was 23%, nitrogen was 2.2%, silicon was 3.1%, and sulfur was 0.1%. X-22-167
The absorption due to the mercapto group near 2560 cm ⁻¹ in the Raman spectrum due to B disappeared.

Example 8 In a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a reflux condenser, 5.00 g (50.0 mm) of methyl methacrylate was added.
ol), 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (5.00 g, 21.0 mmo).
1) and X-22-167B (manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane having a mercapto group introduced at both ends) were charged in an amount of 1.00 g and then dimethyl 2,2-azobis (2-methylpropionate). ) 0.167 g (0.
72 mmol) in n-butyl acetate (26.0 g) was added, the temperature was raised with stirring under a nitrogen atmosphere and the temperature was maintained at 80 ° C. for 3 hours, and then dimethyl 2,2-azobis (2-methylpropionate) 0 was added. 0.167 g (0.72 mmo
3.0 g of n-butyl acetate containing 1) was added, and the mixture was mixed at 90 ° C for 3
The reaction was continued for hours. After cooling to room temperature, 40 g of a colorless transparent solution was obtained. This solution is reprecipitated with hexane, and the obtained precipitate is thoroughly washed with hexane. 40 ~
The solvent and the like are removed by heating and vacuum drying at 50 ° C. for 24 hours. The molecular weight of the obtained product was measured by GPC, and the result was Mn = 10000. As a result of elemental analysis, carbon 61
%, Oxygen 23%, nitrogen 2.3%, silicon 3.1%, and sulfur 0.1%. The absorption due to the mercapto group near 2560 cm ⁻¹ in the Raman spectrum due to X-22-167B disappeared.

(Effect example 1) The resin synthesis used is shown below. (Polymer C: Synthesis of acrylic polyol) In a 2 liter flask equipped with a thermometer, a stirrer, and a reflux condenser, 322 g (3.2 mol) of methyl methacrylate, 102 g (0.78 mol) of 2-hydroxyethyl methacrylate, and 1-dodecanethiol. 86 g of a mixed solution (mixed monomer solution) of 6.1 g (0.03 mol), 400 g of n-butyl acetate, and 3.3 g (0.02 mol) of α, α'-azobisisobutyronitrile were charged, and the temperature was 80 ° C under a nitrogen stream. After heating for 30 minutes, 348 g of the above mixed monomer solution was added over 3 hours, and α, α '
A solution in which 1.6 g (0.01 mol) of azobisisobutyronitrile was dissolved in 35 g of n-butyl acetate was added over 15 minutes, the temperature was raised to 90 ° C., and the polymerization was completed for 3 hours. The obtained solution is used as a polymer C solution (n-butyl acetate 50 wt% solution).
Polymer C has Mn = 7500, Mw = 13000, viscosity 20000 cps
(Viscosity at 20 ° C. was measured with a B type rotational viscometer). Polymer C solution obtained above (n-butyl acetate 50 wt
% Solution) and 100 parts by weight of propylene glycol ethyl ether acetate were added to the solution, and the solid content of the products obtained in Examples 3 and 7 and Tinuvin 292 were added.
(Ciba Geigy Corp. sterically hindered piperidyl group-containing light stabilizer) was added in an amount of 1 part by weight each, and a mixed solution was prepared without the addition. Each of the solutions had a dry film thickness of 3 on an aluminum substrate (A1050P) that had been treated with phosphoric acid
Apply bar coat to 0 μm and in air at 80 ℃ 1
The test plate was dried for a certain period of time. The contact angle of water on the surface of the test plate was measured. Regarding the contact angle, about 0.03 cc of ion-exchanged water was dropped on the surface, and the contact angle was measured within 30 seconds immediately after that. 9 if the products of Examples 3 and 7 were added
It was 2 to 96 degrees, but the other test plates had a low value of 68 to 70. Thus, the products of Examples 3 and 7 increase the water contact angle of the base polymeric material by adding it, whereas Tinuvin 292 has no effect. The nitrogen concentration on the surface of the test plate was measured by X-ray photoelectron spectroscopy (photoelectron escape angle was 90 degrees). The atomic ratio of nitrogen on the surface was found to be in the case of adding the products of Examples 3 and 7. It was 1 to 2 Atom%, but it was not detected in other test plates. Therefore, the products of Examples 3 and 7 are
When added, it has the effect of concentrating the sterically hindered piperidyl groups on the surface of the base polymer material. In contrast, tinuvin 292 has no effect.

(Effect example 2) A solid of the product obtained in Example 3 was added to a solution prepared by adding 100 parts by weight of a polymer C solution (50% by weight solution of n-butyl acetate) and 100 parts by weight of propylene glycol ethyl ether acetate. 17.6 parts by weight of Sumijour N-3500 (polyisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd.) as a curing agent was added to and mixed with a solution containing 1 part by weight of each component and a solution containing no additives. This solution is treated with a phosphoric acid-treated aluminum base material (A
1050P) was coated with a bar coat so that the dry film thickness was 30 μm, and dried in air at 80 ° C. for 1 hour to prepare a test plate. This test plate was subjected to an ultraviolet fluorescent lamp darkness wet test (using a Suga Test Instruments Co., Ltd. Deupanel light control weatherometer DPWL-5R type: UV irradiation 8 hours (70 ° C.) dark wet 4 hours (50 ° C.) cycle) Then, the time when the coating film was cracked was observed. 8 with no additives
It was 00 hours, and the additive of Example 3 was 1600 hours or longer.

[0042]

INDUSTRIAL APPLICABILITY The novel polyorganosiloxane-modified polymer of the present invention has excellent compatibility with solvents and various polymeric materials, and can be concentrated on the surface of polymeric materials with a small amount of addition, and at the same time, has water repellency and water resistance. It is suitable as a stabilizer for polymer materials such as plastics, rubbers, fibers, paints, inks, etc., because it can impart economically and easily the excellent properties of polyorganosiloxane such as properties, chemical resistance and low friction. . In addition, the production method of the present invention makes it possible to obtain a novel polyorganosiloxane-modified polymer by a simple synthetic method.

Claims (8)

[Claims] 1. A monomer having (a) at least one radically polymerizable unsaturated group and at least one sterically hindered piperidyl group in the molecule (or the monomer and another radically polymerizable monomer). Derived (co) polymer unit and (b)
A block or graft polymer characterized by being bonded to a polyorganosiloxane unit via a sulfur atom. 2. (i) One or more of the substituents of the polyorganosiloxane is represented by the following formula (I), and in the other substituents, the side chain substituent is an alkyl group, an aralkyl group, a substituted or unsubstituted group. A group selected from phenyl groups, the main chain terminal group consisting of a trialkylsilyl group,
(Ii) A block or graft polymer having a number average molecular weight of 1,000 to 100,000. —R ¹ —X ¹ —R ² —S—R ³ (I) [In the formula (I), R ¹ is an alkylene which may have a substituent and may contain O or S as a hetero atom. X ¹ represents a single bond, an ester bond, a sulfide bond, an amide bond, a urethane bond, a urea bond, a thiourethane bond, an ether bond or a carbonyl bond, and R ² has a substituent. Or a single bond which may contain O, S, or N of a hetero atom, or R ³ is a compound represented by the following formula (II) -1 or formula (II)-
1 and composed of repeating units represented by (II) -2 (ko)
A polymer unit is shown. Embedded image In formulas (II) -1 and (II) -2, R ⁴ , R ¹¹ , and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Y ¹ , Y ² , and Y ³ Each independently represents a single bond, a substituted or unsubstituted phenylene group, and a group represented by the following structure: Alternatively, these groups represent a group in which the same kind or different kinds of plural groups are bonded, and R ¹⁵ represents an alkylene group having 1 to 22 carbon atoms, a phenylene group, or a group formed by bonding plural kinds of these groups. R ⁵ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, R ^5
6 , R ⁷ , R ⁸ and R ⁹ each independently have 1 to 5 carbon atoms.
Shows an alkyl group which may have a branched structure of. R ¹⁰ is
Indicates a hydrogen atom or a cyano group. R ¹³ and R ¹⁴ are each independently a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms, a phenoxy group, an amino group, or an alkyl group which may be substituted with these groups and which may have a branched structure having 1 to 22 carbon atoms, hydrogen Atom, methyl group, substituted or unsubstituted ring structure group containing O, S, N as a hetero atom, and one or more kinds selected from alkyl groups, aralkyl groups and substituted or unsubstituted phenyl side chains And a main chain terminal group is a trialkylsilyl group. ] 3. The polymer according to claim 1, wherein the polyorganosiloxane is polysilsesquioxane. 4. The polymer according to claim 1, wherein the polyorganosiloxane is polysilsesquioxane and polydialkylsiloxane. 5. The polymer according to claim 1, wherein the polyorganosiloxane is a polydialkylsiloxane. 6. A radical polymerization reaction is carried out in the presence of a mercapto group-containing polyorganosiloxane, a monomer having at least one radically polymerizable unsaturated group and at least one sterically hindered piperidyl group in the molecule. The method for producing a polymer according to claim 1. 7. A monomer having at least one radically polymerizable unsaturated group and at least one sterically hindered piperidyl group in the molecule and a radically polymerizable unsaturated monomer in the presence of a mercapto group-containing polyorganosiloxane. Radical polymerization reaction is performed, The manufacturing method of the polymer of Claims 1-5 characterized by the above-mentioned. 8. A polyorganosiloxane-modified light stabilizer comprising the polymer according to claim 1.