JP2707151B2 - Resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a resin composition, and more particularly, to a non-tacky,
An object of the present invention is to provide a vinyl chloride-based resin composition having excellent migration resistance, bleed resistance, and the like, in addition to lubricity and blocking resistance.

(Prior art) Conventionally, silicon compounds, especially siloxane (silicone) oils, have excellent properties such as non-adhesiveness, lubricity, water repellency, flexibility, heat resistance, etc., and therefore, have defoamers, release agents, fibers. Widely used for applications such as treating agents, various coating agents, paints, inks, and electric / electronic parts.

Attempts have also been made to add functions such as non-adhesion, lubricity, blocking resistance, and stain resistance to the vinyl chloride resin by adding the siloxane compound to the vinyl chloride resin.

(Problems to be Solved by the Invention) However, when a conventional siloxane compound is added to a vinyl chloride resin, the siloxane compound used is temporarily satisfactory in terms of non-adhesion, lubricity and blocking resistance. However, there is a problem that the siloxane compound bleeds out with the passage of time on the surface of the molded article made of the resin composition because of its inherently low compatibility with the vinyl chloride resin, causing various inconveniences.

As a method of solving such a problem, a method of using a siloxane compound having a reactive functional group as a siloxane compound and curing it in a resin composition to eliminate bleed-out has been considered. The siloxane compound having a functional functional group contains a considerable amount of a non-reactive siloxane compound having no active hydrogen group as an impurity, and the bleed-out problem cannot be sufficiently solved.

Of course, it is theoretically possible to purify a siloxane compound having a reactive functional group, but since the physical properties of a non-reactive compound are almost the same as those of a reactive compound, the separation of these non-reactive compounds Is very difficult and not industrial.

Accordingly, an object of the present invention is to provide a siloxane-modified vinyl chloride resin composition which is excellent in migration resistance, bleed resistance and the like in addition to non-adhesion, lubricity and blocking resistance.

(Means for Solving the Problems) The above object is achieved by the present invention described below.

That is, the present invention is characterized in that a siloxane compound having an active hydrogen group and a lactone compound are copolymerized, and a siloxane-modified polyester resin substantially containing no unreacted siloxane compound and a vinyl chloride resin. It is a resin composition.

(Action) The siloxane compound having an active hydrogen group is copolymerized with a lactone compound by subjecting the siloxane compound having an active hydrogen group to a lactone and then subjected to a reduced pressure treatment after the reaction. On the other hand, the non-reactive siloxane compound does not increase in molecular weight, and is thus removed under reduced pressure.

By doing so, the non-reactive siloxane compound contained in the siloxane compound used as a raw material is easily removed, and by mixing such a siloxane-modified polyester resin with a vinyl chloride-based resin, A vinyl chloride resin composition having excellent migration resistance, bleed resistance, and the like in addition to lubricity and blocking resistance is provided.

(Preferred Embodiment) Next, the present invention will be described in more detail with reference to preferred embodiments.

The siloxane-modified polyester resin used in the present invention is obtained by copolymerizing a siloxane compound having an active hydrogen group and a lactone compound, and then subjecting the lactone compound to a vacuum treatment.

Preferred examples of the active hydrogen group-containing siloxane compound used in the present invention include the following compounds.

(1) Amino-modified siloxane oil (M = 1-10, n = 2-10, R = CH ₃ or OCH ₃ ) (M = 1-10, n = 2-10, R = CH ₃ or OCH ₃ , R ′ =
Aliphatic divalent group or aliphatic ether group) (M = 0-200) (N = 2-10) (Branch point = 2-3, R = lower alkyl group, l = 2-20
0, m = 2-200, n = 2-200) (N = 1 to 200, R = lower alkyl group) (N = 1 to 200) (M = 1-10, n = 2-10) (N = 1 to 200) (Branch point = 2-3, R = lower alkyl group, l = 2-20
0, m = 2-200, n = 2-200) (N = 1-10) (M = 1-10, n = 2-10) The above epoxy compound can be used by reacting it with a polyol, polyamine, polycarboxylic acid or the like so as to have an active hydrogen group at a terminal.

(N = 1 to 200) (M = 1-10, n = 2-10, R = aliphatic divalent group or aliphatic ether group) (N = 0 to 200) (L = 1-10, m = 10-200, n = 1-5) (N = 1 to 200, R = lower alkyl) (R = lower alkyl group, R ′ = hydrogen atom, alkyl group,
K = 1-250, l = 0-5, m = 0-50, n = 1-5) (R = lower alkyl group, R ′ = hydrogen atom, alkyl group,
k = 1-250, l = 0-5, m = 0-50, n = 2-5) (M = 1-10, n = 2-10) (N = 2-10) (Branch point = 2-3, R = lower alkyl group, l = 2-20
0, m = 2-200, n = 2-200) (N = 1 to 200, R = lower alkyl group) (5) Carboxyl-modified siloxane oil (M = 1-10, n = 2-10) (N = 1 to 200) (Branch point = 2-3, R = lower alkyl group, l = 2-20
0, m = 2-200, n = 2-200) (N = 1 to 200, R = lower alkyl group) The siloxane compound having an active hydrogen group as described above is
It is an example of a preferred siloxane compound in the present invention, the present invention is not limited to these examples,
The compounds exemplified above and other siloxane compounds are
It is currently commercially available and can be easily obtained from the market, and any of them can be used in the present invention.

In the present invention, the lactone compound to be reacted with a siloxane compound having an active hydrogen group is a lactone compound capable of forming a polyester by conventional lactone ring-opening polymerization, such as ε-caprolactone, δ-valerolactone, and the like. Mono- or di-substituted derivatives such as alkyl, halogen, haloalkyl, alkoxy and alkoxyalkyl can be used as well. Particularly preferred lactone compounds are ε-caprolactone and derivatives thereof.

The reaction between the siloxane compound and the lactone compound is carried out by mixing the two, preferably using a suitable catalyst under a nitrogen stream, and reacting at a temperature of 150 to 200 degrees for several hours to several tens of hours, The desired siloxane-modified polyester copolymer is obtained.

Both can be reacted at any reaction ratio, but for the purpose of the present invention, it is preferable to carry out the reaction so that the siloxane segment accounts for 5 to 80% by weight in the obtained copolymer. If the amount of the siloxane compound is too small, the non-adhesiveness of the finally obtained resin composition,
Blocking resistance and the like become insufficient. On the other hand, when the amount is too large, the film forming property and the film strength of the obtained resin composition decrease, which is not preferable.

The copolymer obtained as described above contains the non-reactive siloxane compound contained in the siloxane compound used as it is, and varies depending on the siloxane compound used and the copolymerization ratio. About 1.0 of copolymer
It is contained as an impurity in a proportion of about 5% by weight.

Such impurities are difficult to separate at the raw material stage,
In the present invention, it is easily removed by performing a reduced pressure treatment at a temperature of about 100 to 250 ° C. continuously or preferably at a temperature of about 10 mmHg, preferably 5 mmHg or less under an inert atmosphere such as nitrogen gas after the copolymerization. Thus, a polyester resin containing substantially no unreacted siloxane compound is obtained. In the present invention, the term "substantially not contained" means that the content of the unreacted siloxane compound is less than 1.0%.

The polyester resin as described above may be of any molecular weight, but preferably has a molecular weight of about 1,000 to 30,000 in consideration of usability, and the molecular weight may be adjusted by a known technique as it is. Further, the copolymer has a reactive hydroxyl group at a terminal, and these terminal groups may be left as they are, but may be blocked with a blocking agent such as acetic anhydride, or various cross-linking agents. (Curing agent) can be crosslinked (cured).

The vinyl chloride resin used in the present invention includes a vinyl chloride homopolymer, a vinylidene chloride homopolymer, a copolymer of vinyl chloride or vinylidene chloride with various other copolymerizable monomers, or a terpolymer. Polymers. Examples of copolymerizable monomers include, for example, vinyl esters, vinyl ethers, vinylidene chloride, lower olefins, aromatic vinyl compounds such as vinyl acetate, vinyl bromide, vinyl fluoride, styrene, heterocyclic vinyl compounds such as vinyl pyridine, and acrylic. Acids and derivatives thereof, and conjugated diene compounds such as butadiene are exemplified.

Further, the vinyl chloride resin as described above may be a blend with another polymer such as a styrene-acrylonitrile copolymer and a styrene-methyl methacrylate copolymer.

The mixing ratio of the siloxane-modified polyester resin and the vinyl chloride resin is not particularly limited and may vary depending on the purpose of use, but the former: the latter are in a weight ratio of 200: 10 to 10:20.
0, preferably in the range 200: 100 to 100: 200. The mixing of the two may be simply the mixing of the powders, but it is preferred that they are melt-kneaded with a mixing roll, an extruder or the like and homogenized.

Further, the resin composition is a stabilizer such as a metal soap of other fatty acids, a coloring agent, a plasticizer, an antistatic agent, an ultraviolet absorber,
Conventional additives such as foaming agents can also be included.

The resin composition of the present invention as described above is very useful as various molding materials, synthetic leather materials, fiber coating agents, surface treatment agents, formation of release layers such as release papers, paints, binders for printing inks, and the like. .

(Examples) Next, the present invention will be described more specifically with reference to examples, comparative examples, and evaluation examples. In the description, parts and% are based on weight unless otherwise specified.

Example 1 (M and n are values at which the amine equivalent becomes 3,800) A reactor equipped with a stirrer, a thermometer, a nitrogen gas inlet tube and a reflux condenser has 240 parts of ε-caprolactone and the above structure (1). 100 parts of the amino-modified siloxane oil and 0.05 parts of tetrabutyl titanate were charged, and the mixture was reacted at a temperature of 180 ° C. for 10 hours under a nitrogen stream. As the reaction proceeds, the viscosity of the reaction product increases.

Thereafter, the reaction was continued at 180 ° C. under a reduced pressure of 5 mmHg for 1 hour to complete the reaction and completely remove the non-reactive siloxane compound and unreacted substances contained in the starting siloxane compound. The unreacted siloxane compound removed was 12 parts.

Thereafter, 15 parts of acetic anhydride was added at 140 ° C., and the mixture was reacted under reflux for 1 hour to completely acetylate the hydroxyl groups in the product. At the same temperature, by-product acetic acid and unreacted acetic anhydride were removed under reduced pressure at 5 mmHg.

The product obtained is a waxy polysiloxane having a melting point of 78 ° C.
It is a polyester copolymer.

Then 80 parts of the above product, vinyl chloride resin with a polymerization degree of 1050
100 parts, 1.3 parts of calcium stearate and 1.3 parts of zinc stearate were kneaded for 12 minutes on a 165 ° C heating roll to obtain a sheet-shaped resin composition of the present invention. The kneaded sheet was further placed in a hot press at 175 ° C. and hot pressed at a pressure of 200 kg / cm ² for 5 minutes to obtain a test sheet having a thickness of about 1 mm.

Example 2 (M and n are values at which the amine equivalent becomes 3,500) In the same manner as in Example 1, 160 parts of ε-caprolactone,
140 parts of amino-modified siloxane oil having the above structure (2) and 0.04 part of tetrabutyl titanate are charged,
The reaction was performed at a temperature of 180 ° C. for 10 hours under a nitrogen stream. As the reaction proceeds, the viscosity of the reaction product increases.

Thereafter, the reaction was continued at 180 ° C. under a reduced pressure of 5 mmHg for 1 hour to complete the reaction and completely remove the non-reactive siloxane compound and unreacted substances contained in the starting siloxane compound. Unreacted siloxane compound removed was 15 parts.

Thereafter, 15 parts of acetic anhydride was added at 140 ° C., and the mixture was reacted under reflux for 1 hour to completely acetylate the hydroxyl groups in the product. At the same temperature, by-product acetic acid and unreacted acetic anhydride were removed under reduced pressure at 5 mmHg.

The product obtained is a waxy polysiloxane having a melting point of 76 ° C.
It is a polyester copolymer.

Then 80 parts of the above product, vinyl chloride resin with a polymerization degree of 1050
100 parts, 1.3 parts of calcium stearate and 1.3 parts of zinc stearate were kneaded on a heating roll at 165 ° C. for 12 minutes to obtain a sheet-shaped resin composition of the present invention. The kneaded sheet was further placed in a hot press at 175 ° C. and hot-pressed at a pressure of 200 kg / cm ² for 5 minutes to obtain a test sheet having a thickness of about 1 mm.

Example 3 (M and n are values at which the hydroxyl value becomes 25) In the same manner as in Example 1, 200 parts of ε-caprolactone,
160 parts of alcohol-modified siloxane oil having the above structure (3) and 0.05 part of tetrabutyl titanate were charged and reacted at 180 ° C. for 10 hours under a nitrogen stream. As the reaction proceeds, the viscosity of the reaction product increases.

Thereafter, the reaction was continued at 180 ° C. under a reduced pressure of 4 mmHg for 1 hour to complete the reaction and completely remove nonreactive siloxane compounds and unreacted substances contained in the starting siloxane compound. The unreacted siloxane compound removed was 12 parts.

Thereafter, 20 parts of acetic anhydride at 140 ° C. was added, and the mixture was reacted under reflux for 1 hour to completely acetylate the hydroxyl groups in the product. At the same temperature, by-product acetic acid and unreacted acetic anhydride were removed under reduced pressure at 5 mmHg.

The product obtained is a waxy polysiloxane having a melting point of 78 ° C.
It is a polyester copolymer.

Then 80 parts of the above product, vinyl chloride resin with a polymerization degree of 1050
100 parts, 1.3 parts of calcium stearate and 13 parts of zinc stearate were kneaded in a tube on a 165 ° C heating roll for 12 minutes to obtain a sheet-shaped resin composition of the present invention. The kneaded sheet was further placed in a hot press at 175 ° C. and hot pressed at a pressure of 200 kg / cm ² for 5 minutes to obtain a test sheet having a thickness of about 1 mm.

Example 4 (M and n are values at which the hydroxyl value becomes 32) In the same manner as in Example 1, 180 parts of ε-caprolactone,
160 parts of alcohol-modified siloxane oil having the above structure (4) and 0.04 part of tetrabutyl titanate were charged and reacted at 180 ° C. for 10 hours under a nitrogen stream. As the reaction proceeds, the viscosity of the reaction product increases.

Thereafter, the reaction was continued at 180 ° C. under a reduced pressure of 5 mmHg for 1 hour to complete the reaction and completely remove the non-reactive siloxane compound and unreacted substances contained in the starting siloxane compound. The removed unreacted siloxane compound was 10 parts.

Thereafter, 16 parts of acetic anhydride was added at 140 ° C., and the mixture was reacted under reflux for 1 hour to completely acetylate the hydroxyl groups in the product. At the same temperature, by-product acetic acid and unreacted acetic anhydride were removed under reduced pressure at 5 mmHg.

The product obtained is a waxy polysiloxane having a melting point of 75 ° C.
It is a polyester copolymer.

Then 80 parts of the above product, vinyl chloride resin with a polymerization degree of 1050
100 parts, 1.3 parts of calcium stearate and 1.3 parts of zinc stearate were kneaded on a heating roll at 165 ° C. for 12 hours to obtain a sheet-shaped resin composition of the present invention. The kneaded sheet was further placed in a hot press at 175 ° C. and hot-pressed at a pressure of 200 kg / cm ² for 5 minutes to obtain a test sheet having a thickness of about 1 mm.

Comparative Examples 1 to 4 A resin composition was prepared with the following composition, and a test sheet having a thickness of about 1 mm was obtained in the same manner as in the examples.

Comparative Example 1 DOP 80 parts Vinyl chloride resin (degree of polymerization 1050) 100 parts Calcium stearate 1.3 parts Zinc stearate 1.3 parts Comparative Example 2 Polyester plasticizer (average molecular weight 2000, manufactured by Dainichi Seika Kogyo Co., Ltd.) 80 parts Vinyl chloride Resin (degree of polymerization 1050) 100 parts Calcium stearate 1.3 parts Zinc stearate 1.3 parts Comparative Example 3 DOP 72 parts Silicone oil 8 parts Vinyl chloride resin (degree of polymerization 1050) 100 parts Calcium stearate 1.3 parts Zinc stearate 1.3 parts Comparative Example 4 Polyester 72 parts Silicone oil 8 parts Vinyl chloride resin (degree of polymerization 1050) 100 parts Calcium stearate 1.3 parts Zinc stearate 1.3 parts Silicone oil is vinyl chloride resin If more than 8 parts is added to 100 parts, processing is difficult under the above processing conditions and homogeneous vinyl chloride is used. Resin sheet was not obtained.

Evaluation Examples When various physical properties of the test sheets of the above Examples and Comparative Examples were measured, the results shown in Table 1 below were obtained.

(Effect) According to the present invention as described above, a vinyl chloride-based resin composition having excellent migration resistance, bleed resistance, and the like in addition to non-adhesion, lubricity, and blocking resistance is provided.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Katsumi Kuriyama, Inventor 1135-1 Kuri Shimoma, Koshigaya City, Saitama Prefecture (56) References JP-A-59-207922 (JP, A) JP-A-47-5694 (JP, A Japanese Patent Publication No. Sho 62-501848 (JP, A) Japanese Patent Publication Sho 46-43306 (JP, B1)

Claims (2)

(57) [Claims] A siloxane compound having an active hydrogen group and a lactone compound are copolymerized, comprising a siloxane-modified polyester resin substantially free of unreacted siloxane compound and a vinyl chloride resin. Resin composition. 2. A copolymer having 5 to 5 siloxane segments.
The resin composition according to claim 1, which accounts for 80% by weight.