JP3409481B2 - Method for modifying resin with terminal isocyanate siloxane - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has no problems such as gelling or set-off of a resin, and is advantageous in industrially modifying a resin with isocyanate siloxane at one end. To a method for modifying a resin with an isocyanate siloxane having one terminal. 2. Description of the Related Art A method for modifying a resin with an isocyanate siloxane at one end is disclosed in Japanese Patent Publication No. 4-41693, in which carbinol siloxane at one end is converted to HDI (here, HDI). Is an abbreviation of hexamethylene diisocyanate, which has been exemplified as an example of a diisocyanate, but examples of usable diisocyanates other than HDI include tolylene diisocyanate, isophorone diisocyanate, and methylene bisphenyl isocyanate. A method of deriving siloxane and modifying the resin with this compound has been proposed. However, in the above method, since HDI remains due to excessive use of HDI, when a modified resin is synthesized using a resin having a large number of isocyanate-reactive functional groups in the side chain, impurities may be present. There was a problem of gelling of the resin due to. In addition, in this method, unless HDI is used in a large excess, a siloxane compound in which carbinol siloxane is added to both of the two isocyanates of HDI and which does not react with the resin is by-produced. When a modified resin is synthesized to form a roll by utilizing the same, unreacted silicone is transferred to the surface as a result, and there is a disadvantage that set-off problem occurs. [0004] Therefore, it is desired to develop a method of modifying a resin with a one-terminal isocyanate siloxane which does not have the above-mentioned problems. SUMMARY OF THE INVENTION The present invention has been made to meet the above-mentioned demands, and provides a modified resin having no problem of gelling or set-off of the resin, and having a good surface slip property, and is industrially advantageous in that the isocyanate siloxane having one end is advantageous. It is an object of the present invention to provide a method for modifying a resin by the method. The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that one-terminal hydrogenenesiloxane represented by the following general formula (I):
A fragment having one isocyanate group and at least one unsaturated hydrocarbon group in one molecule and obtained by an addition reaction with an isocyanate group-containing organic silicon compound represented by the following general formula (II): It has been found that by modifying a resin having a group capable of reacting with an isocyanate group in a side chain using a terminal isocyanate siloxane, the resin can be satisfactorily modified with one-terminal isocyanate siloxane. [0007] [0008] That is, the present inventor has disclosed in Japanese Patent Laid-Open No. 6-25666.
No. 1 proposed a method for synthesizing one-terminal isocyanate siloxane using m-isopropenyl-α, α-dimethyl isocyanate (m-TMI). If the reactivity is poor and the reactivity is poor, 50
It took more than an hour. On the other hand, the method for synthesizing the one-terminal isocyanate siloxane according to the present invention is as follows.
-The time required for the addition reaction is shorter than in the case of using TMI, the addition reaction is completed within 10 hours, and impurities (diisocyanate compound, isocyanate-free siloxane compound) which are problematic when synthesizing the modified resin Is low, and there is no by-product of a siloxane compound that does not react with the resin, and an excellent isocyanate siloxane having one terminal is obtained. Therefore, the method for modifying a resin with one-terminal isocyanate siloxane of the present invention does not cause the problem of gelling of the resin due to impurities or the problem of set-off due to unreacted silicone, and also provides a modified resin having excellent surface slipperiness. It can be produced industrially advantageously. Accordingly, the present invention provides a hydrogen siloxane having one end represented by the above general formula (I), one isocyanate group and at least one unsaturated group in one molecule represented by the above general formula (II). It is characterized in that a resin having a group capable of reacting with an isocyanate group in a side chain is modified by using an isocyanate group having an isocyanate group, which is obtained by performing an addition reaction with an isocyanate group-containing organic silicon compound having a hydrocarbon group. And a method for modifying a resin with a one-terminal isocyanate siloxane. Now, the present invention will be described in further detail. The first invention of the method for modifying a resin with one-terminal isocyanate siloxane according to the present invention comprises a one-terminal hydrogen siloxane represented by the following general formula (I) and one molecule One-terminal isocyanate siloxane having one isocyanate group and at least one unsaturated hydrocarbon group therein and obtained by an addition reaction with an isocyanate group-containing organosilicon compound represented by the following general formula (II): To modify a resin having a group capable of reacting with an isocyanate group in a side chain. [0013] Embedded image In the above-mentioned formula (I), R ^{1 to} R ⁷ are, for example, alkyl groups such as methyl, ethyl, propyl and butyl, alkenyl groups such as vinyl and allyl, and aryl groups such as phenyl group. Groups, aralkyl groups such as benzyl group, and halogenated hydrocarbon groups in which some or all of these groups have been substituted with halogen atoms, but are preferably groups having no aliphatic unsaturated bond. Further, n is an integer of 1 or more.
150 is preferred. If n is less than 10, the surface properties obtained by siloxane modification may not be sufficient,
If it exceeds 150, the grafting reaction of the siloxane to the resin may be slow or difficult. On the other hand, in the isocyanate silicone compound of the formula (II), R ^{8 to} R ¹² are the same as the above R ^{1 to} R ^{12
The same} groups as the groups exemplified in ⁷ can be mentioned, but at least one of them is an aliphatic unsaturated group such as an alkenyl group. R ¹³ has 1 to 12 carbon atoms, preferably 1
In the above-mentioned divalent hydrocarbon groups, there may be mentioned an alkylene group, an arylene group and the like, and a group in which some or all of the hydrogen atoms are substituted with halogen atoms. M is an integer of 0 or more, preferably 0 to 3. Specific examples of such an isocyanate silicone compound include the following compounds (where Me is a methyl group; the same applies hereinafter). Embedded image Embedded image The addition reaction between the one-terminal hydrogen siloxane of the above formula (I) and the isocyanate silicone compound of the above formula (II) can be carried out by a known method using a platinum catalyst. In the above addition reaction, a reaction solvent may not be used.
Ether-based, aliphatic hydrocarbon-based, and aromatic hydrocarbon-based solvents are preferably used. The amount of the solvent used is preferably about 1/2 to 2 times the amount of hydrogen siloxane at one end. The platinum-based catalyst may be a known catalyst that is used in a usual hydrosilation reaction, but chloroplatinic acid or a derivative thereof is preferable. And a complex with vinyl siloxane. The amount of the platinum-based catalyst used may be a catalytic amount, and is preferably 0.1 to 1000 ppm. Further, in the above reaction, the reaction temperature is from 0 to
200 ° C., particularly preferably 50 to 120 ° C., is suitable, and the reaction time is usually sufficient within 10 hours. ００２７ ００２９ ００２９ ００２９ ００２９ ００２９ ００４２ ００２９ ００３７ ００３６ ００３６ ００３６ ００３７ ００３７ ００３７ ００３７ ００４２ ００４２ ００４２ ００４２ ００４２. In the present invention, the resin is modified using the thus obtained isocyanate siloxane at one end.
In this case, various resins can be used as long as the resin has a group capable of reacting with an isocyanate group in a side chain. Specifically, acetal resin, polyester polyol resin, cellulose resin, epoxy polyol resin, polyurethane polyol resin, polyurethane resin, polyester urethane resin, polyether urethane resin, acrylic polyol resin, polyvinyl alcohol resin, ethylene / vinyl alcohol resin, vinyl chloride /
Examples thereof include a vinyl acetate / vinyl alcohol copolymer and a polycarbonate polyol resin. The reaction between the one-terminal isocyanate siloxane and the resin can be carried out in the same manner as in the modification of a resin with an ordinary isocyanate compound. The one-terminal isocyanate siloxane and the resin are converted into OH, NH ₂ , SH groups and the like of the resin. At a ratio such that the number of moles of isocyanate is smaller than that of active hydrogen at room temperature to 150 ° C., particularly 50 to 100 ° C.
The reaction is desirably performed at 1 ° C. for 1 to 10 hours, particularly 2 to 5 hours. If the one-terminal isocyanate compound is used more than the number of moles of active hydrogen, it may be necessary to remove unreacted substances. Although the above reaction does not require the use of a solvent,
It is desirable to use a solvent from the viewpoint of mixing with the resin, reaction efficiency, and reaction control. As the solvent, for example, toluene without active hydrogen, xylene, dibutyl ether,
It is desirable to use ethyl acetate, hexane and the like. The amount of the solvent to be used is not particularly limited, but may be from the same amount as the resin to 1%.
It is preferably about 0 times. Further, although the reaction proceeds without using a catalyst, it is desirable to add a catalyst in order to complete the reaction in a short time. As the catalyst, those usually used in the production of polyurethane are preferable, and specific examples thereof include organic tin compounds such as dibutyltin dilaurate and dibutyltin dioctate, triethylamine, N-ethylmorpholine, N,
Tertiary amines such as N, N ', N'-tetramethyl-1,3-butanediamine and 1,4-diazabicyclo (5.4.0) undecene-7 are exemplified. These catalysts are used in an amount of 0.01 to one end isocyanate siloxane.
-20% by weight, especially 0.1-2% by weight is preferred. According to the method of modifying a resin with a one-terminal isocyanate siloxane according to the present invention, a modified resin having good surface slipperiness without the problem of gelling or set-off of the resin is industrially advantageous. Can be manufactured. Hereinafter, the present invention will be described specifically with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. Synthesis Example 1 37.2 g (0.22 mol) of the compound represented by the following formula (1) was charged into a flask equipped with a dropping funnel, a cooling tube, a thermometer, and a stirrer, and charged under a nitrogen stream. ° C, and 16.4 mg of chloroplatinic acid
After adding (2 × 10 ⁴ mol), 304 g (0.2 mol) of a compound represented by the following formula (2) was added dropwise at a temperature of 70 to 80 ° C. After dropping, the mixture was aged at 80 to 90 ° C for 5 hours.
When the remaining iH was quantified, the reaction rate was 97%. Embedded image When the obtained light brown transparent liquid was identified by NMR and elemental analysis, it was confirmed to be a compound represented by the following formula (3). Embedded image [Synthesis Example 2] 53.5 g of a compound represented by the following formula (4) (0.2
2 mol), and reacted similarly. After aging for 5 hours, the conversion was 97%. Embedded image When the obtained light brown transparent liquid was identified by NMR and elemental analysis, it was confirmed to be a compound represented by the following formula (5). Embedded image Example 1 An acetal comprising a vinyl butyral / vinyl alcohol / vinyl acetate copolymer was placed in a flask equipped with a dropping funnel, a cooling tube, a thermometer, and a stirrer. Resin / Slek BX-1 (Sekisui Chemical Co., Ltd.) 100
g, 300 g of ethyl acetate, 300 g of toluene and 0.1 g of dibutyltin dilaurate, and after dissolving the resin at 70 ° C., 10 g of the one-terminal isocyanate siloxane represented by the above formula (3) obtained in Synthesis Example 1 was added dropwise. , 7
The reaction was performed at 0 to 80 ° C for 6 hours. When the residual isocyanate was quantified, the reaction rate was 96%. [Example 2] Acrydic A-817 (manufactured by Dainippon Ink and Chemicals, Inc.) 20 instead of Esrec BX-1
0 g (MMA / styrene / HEMA copolymer, solid content 5
0%), except that denaturation was carried out in the same manner as in Example 1. The reaction rate after 6 hours' reaction was 97%. Example 3 Polyester polyol resin Adecane Ace F15-2 consisting of adipic acid / ethylene glycol condensate instead of S-LEC BX-1
Modification was carried out in the same manner as in Example 1 except that 100 g of 0 (manufactured by Asahi Denka Co., Ltd.) was used. The reaction rate after 6 hours' reaction was 97%. Example 4 Modification was carried out in the same manner as in Example 1 except that the compound represented by the above formula (5) obtained in Synthesis Example 2 was used as the one-terminal isocyanate siloxane. The reaction rate after 6 hours of reaction was 98%. [Comparative Example 1] A compound represented by the following structural formula (10) (HD
Modification was carried out in the same manner as in Example 1 except that 10 g of (I to 0.5 mol excess of siloxane) was used. The isocyanate siloxane thickened during the addition and gelled. Embedded image [Comparative Examples 2 to 4]
The resin used in 3 was directly dissolved in ethyl acetate / toluene without reacting with the isocyanate siloxane at one end to prepare a sample for evaluation. The surface characteristics of the obtained sample were evaluated by the following methods. Table 1 shows the results. Evaluation method of surface characteristics: The samples obtained in the above Examples and Comparative Examples were applied to glass and dried, and the contact angle of water was measured. In addition, after coating on a PET film and drying, another PET film is superimposed on the coated surface, and the applied amount is 20 g / cm.
After being left at 60 ° C./48 hours under a load of ² , the surface tension of the transfer surface was measured with a wetting index standard solution. From the results shown in Table 1, it can be seen that the modified resin with one-terminal isocyanate siloxane obtained by the production method of the present invention is a good modified siloxane resin which does not gel during the modification and has no set-off property. It was revealed. [Table 1]

──────────────────────────────────────────────────続 き Continuing from the front page (72) Akira Yamamoto, Inventor, 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Inside the Silicone Electronics Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (56) References JP-A-6-116390 ( JP, A) JP-A-6-228161 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 77/00-77/62 C08L 83/00-83/16

Claims (1)

(57) Claims 1. One-terminal hydrogen siloxane represented by the following general formula (I), one isocyanate group and at least one aliphatic unsaturated hydrocarbon in one molecule. Having a group capable of reacting with an isocyanate group in a side chain using an isocyanate siloxane having one end obtained by an addition reaction with an isocyanate group-containing organic silicon compound represented by the following general formula (II) A method for modifying a resin with one-terminal isocyanate siloxane, which comprises modifying the resin. Embedded image Embedded image