Complex microspheres, method of making same, and thermoplastic films containing same

A thermoplastic film containing complex microspheres, of which the average diameter if 0.1.about.3 .mu.m, the standard deviation of particle size is 1.0.about.2.0 and the ratio of major and minor axes is 1.0.about.1.1, said complex microspheres being contained by 0.005.about.5 weight % in said thermoplastic film, said complex microspheres consisting of polysiloxane and vinyl polymer, said polysiloxane and vinyl polymer being unistructurally mixed together and being substantially free of covalent bonds therebetween, said polysiloxane and vinyl polymer being contained at ratio of 97/3.about.30/70 by weight, the average diameter of said complex microspheres being 0.05.about.30 .mu.m, the standard deviation of particle size of said complex microspheres being 1.0.about.2.5, and the ratio between the major and minor axes of said complex microspheres being 1.0.about.1.2, said complex microspheres being produced by the steps of causing polycondensation of silanol group-forming compound while said silanol group-forming compound undergoes hydrolysis in the absence of emulsifier inside an aqueous solvent containing said silanol-group forming compound and water-insoluble vinyl monomer at weight ratio of 99/1.about.33/67 under the condition of two layer system of said aqueous solvent and water-insoluble contents consisting of said silanol group-forming compound and water-insoluble vinyl monomer, thereby generating polysiloxane microspheres, impregnating said water-insoluble vinyl monomer into said polysiloxane microspheres to form polysiloxane microspheres mixed with said water-insoluble vinyl monomer, and polymerizing said water-insoluble vinyl monomer mixed in said polysiloxane microspheres in the presence of a radical initiator, thereby obtaining said complex microspheres, said silanol group-forming compound being of the form of Formula (1) or (2) and containing at least 15 mole % (converted to silicon quantity) of compounds of form R.sup.1 -SiX.sub.3 and/or compounds of form SiX.sub.4, and said water-insoluble vinyl monomer comprising one or more kinds which are not reactive with silanol group and silanol group-forming atoms, where said Formula (1) is R.sup.1.sub.p -SiX.sub.4-p, and said Formula (2) is ##STR3## p is an integer 0.about.3;

• q is an integer 3.about.20;
• R.sup.1, R.sup.2 and R.sup.3 are non-substituted or substituted hydrocarbon groups having a carbon atom directly connected to a silicon atom and no tendency to undergo radical polymerization;
• and X is alkoxy group with 1.about.4 carbon atoms, alkoxyethoxy group having alkoxy group with 1.about.4 carbon atoms, acyloxy group with 2.about.4 carbon atoms, N,N-dialkylamino group having alkyl group with 1.about.4 carbon atoms, hydroxyl group, halogen atom, or hydrogen atom.

A method of making complex microspheres consisting of polysiloxane and vinyl polymer, said method comprising the steps of causing polycondensation of silanol group-forming compound while said silanol group-forming compound undergoes hydrolysis in the absence of emulsifier inside an aqueous solvent containing said silanol-group forming compound and water-insoluble vinyl monomer at weight ratio of 99/1.about.33/67 under the condition of two layer system of said aqueous solvent and water-insoluble contents consisting of said silanol group-forming compound and water-insoluble vinyl monomer, thereby generating polysiloxane microspheres, impregnating said water-insoluble vinyl monomer into said polysiloxane microspheres to form polysiloxane microspheres mixed with said water-insoluble vinyl monomer, and polymerizing said water-insoluble vinyl monomer mixed in said polysiloxane microspheres in the presence of a radical initiator, thereby obtaining said complex microspheres, said silanol group-forming compound being of the form of Formula (1) or (2) and containing at least 15 mole % (converted to silicon quantity) of compounds of form R.sup.1 -SiX.sub.3 and/or compounds of form SiX.sub.4, and said water-insoluble vinyl monomer comprising one or more kinds which are not reactive with silanol group and silanol group-forming atoms, where said Formula (1) is R.sup.1.sub.p -SiX.sub.4-p ;

• said Formula (2) is ##STR4## p is an integer 0.about.3;
• q is an integer 3.about.20;
• R.sup.1, R.sup.2 and R.sup.3 are non-substituted or substituted hydrocarbon groups having a carbon atom directly connected to a silicon atom and no tendency to undergo radical polymerization;
• and X is alkoxy group with 1.about.4 carbon atoms, alkoxyethoxy group having alkoxy group with 1.about.4 carbon atoms, acyloxy group with 2.about.4 carbon atoms, N,N-dialkylamino group having alkyl group with 1.about.4 carbon atoms, hydroxyl group, halogen atoms, or hydrogen atom.