JPS5930848A - Preparation of acrylic resin molded article having modified surface property - Google Patents

Abstract

PURPOSE:To obtain a molded article having excellent surface characteristics, and imparted with water and oil repellency, releasability, low frictional property, stain-proofing property, etc., by adding a polymerizable compound containing a perfluoroalkyl group and a radical polymerization initiator to an acrylic resin, and molding the composition under melting. CONSTITUTION:An acrylic resin is mixed with a polymerizable compound containing a perfluoroalkyl grup and a radical polymerization initiator, and molded under melting. The polymerizable compound is preferably the compound of formula I or II (Rf is 3-20C fluoroalkyl or perfluoroalkyl; R1 is 1-5C alkyl; R2 and R4 are 1-20C alkylene; R3 and R5 are H or methyl). The radical polymerization initiator is an organic peroxide or an azo compound. The amount of the polymerizable compound is 0.1-5pts.wt., preferably 0.25-1pt.wt. per 100pts. wt. of the acrylic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an acrylic resin molded article with modified surface properties.

Modification of surface properties in the present invention mainly refers to lowering the surface energy of the resin. In other words, the specific effects are water and oil repellency, non-adhesiveness, low friction properties, etc., but also improvements in button resistance, stain resistance, reduction of water absorption, and improvement of WL characteristics. ) Various effects such as a reduction in the r71 refractive index can be obtained.

Adding a perfluoroalkyl group-containing compound to sealant,
A composition having self-releasing property and self-lubricating property,
It is already known to impart water and oil repellency and low friction properties to the outer surface of the 17ir.
man et al. I & E, C, Product fte
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Development 86.4 (1965) "C1 polyvinylidene chloride, vinyl chloride-vinyl chloride copolymer, acrylic (in contrast to the ester compound containing a perfluoroalkyl group in nails). However, it has been reported that the perfluoroalkyl group-containing compound diffuses over the surface of the resin, leaving only the surface with fluorine debris (not exhibiting full water and oil repellency or decreasing the coefficient of friction.However, this method It is stated that the amount of the compound used is relatively large, and that in the case of acrylic resin, the amount of the compound added is white and only one drop is produced.

According to the 1vf theory of the present inventors, even if various known or well-known fluorinated surfactants, etc., including perfluoro°rkyl group-containing ester compounds, etc. are simply kneaded into acrylic resin, the overall No change in surface properties was observed unless large amounts were added.

In addition, the present inventors have found that when a polymerizable compound containing a perfluoroalkyl group and a radical polymerization initiator such as an organic peroxide diazo compound are combined, mixed with a resin, and melt-molded, the perfluoroalkyl group It was discovered that polymerization of the monomer occurs, resulting in a decrease in compatibility with the resin, making the surface of the resin appear as if it were coated. Therefore, in the warehouse where the acrylic sesame resin is molded, the perfluoroalkyl group-containing monomer-v-f is dispersed in the molten starch resin, and the perfluoroalkyl group-containing monomer is subjected to appropriate KM reaction in the presence of an appropriate polymerization initiator. It was found that if this method were used, it would be possible to quickly produce a molded article in which a surface layer of perfluoroalkyl groups was efficiently formed while maintaining appropriate compatibility with the resin.

Based on this knowledge, the present inventors further studied the quantitative relationship between the above-mentioned perfluoroalkyl group-containing polymerizable compound and the radical polymerization initiator to be added, and arrived at the present invention. That is, the gist of the present invention is a patented method for producing a molded article, which is characterized in that a polymerizable compound containing a perfluoroalkyl group and a radical polymerization initiator are added to an acrylic resin, mixed, and then melt-molded. ,It is in.

The acrylic resin to be used in the present invention is not limited to @Ic, but resins with good flow characteristics such as injection molding grade and extrusion molding grade are suitable. Compounds containing perfluoroalkyl groups that can be added to such acrylic resins have the following general formula (in the formula R (is a fluoroalkyl group or perfluoroalkyl group having 3 to 20 carbon atoms, RI is an alkyl group having 1 to 5 carbon atoms b, Rl+'R4 is an alkylene group having 1 to 20 carbon atoms, R8eRl is a hydrogen atom or a methyl group ) is an acrylate or methacrylate represented by R R! is a fluoroalkyl group, R! is an alkyl group having 1 to 3 carbon atoms, and R!
It is particularly preferred that R4 is an alkylene group having 2 to 4 carbon atoms.The amount of the polymerizable compound containing a perfluoroalkyl group added is 0.1 to 100 parts by weight of the acrylic resin. In the range of 5.0 parts by weight, preferably 0
, 25-1. This is the range of Offi piece. Addition amount is 0.
If the amount is less than 1 part by weight, the modification effect will be a little slow, and if it exceeds 5.0 parts by weight, the surface energy lowering ability will reach a certain level and even if the addition ik is increased, the surface energy lowering ability will no longer be improved. It has been found that this is disadvantageous for a wide range of commercial activities, as the resin composition is not visible and the resin composition becomes cloudy.

Further, the polymerization initiator used in the present invention is not particularly limited as long as it is an initiator that can be incorporated into normal radical polymerization. For example, various radical polymerization initiators such as organic peroxides and azo compounds, or ionizing radiation such as r-rays are employed. Specifically, as the organic peroxide, benzoyl peroxide, cumenoyl peroxide, di-tert-butyl peroxide, and as an azo compound, 'C is α, α'-azobisinbutyronitrile is preferable. .

The amount of these polymerization initiators to be added is 0.4 to 5.0 polymerizable with respect to the perfluoroalkyl group-containing polymerizable compound.
H, preferably in the range of 1.0 to 3.0% by weight. If the amount added is less than 0.4% by weight, no decrease in surface energy will be observed unless the perfluoroalkyl group-containing acrylate (methacrylate) is added in an amount of 5.0 parts by weight or more based on the acrylic resin button.

In that case, the resin composition may further discolor.
The transparency and aesthetics unique to acrylic resin will be impaired.

The method for molding the resin in the present invention is preferably a melt molding method using a hot press, considering the so-called aging time required for appropriate polymerization of the perfluoroalkyl group-containing polymerizable compound and diffusion to the surface of the molded product. be. The molding temperature is 180 to 240°C, the molding time is 1 to 4 hours, and the present invention achieves the desired surface properties by using the above-mentioned compound in combination with a perfluoroalkyl group-containing compound and a radical polymerization initiator. This makes it possible to significantly reduce the degree of addition of the perfluoroalkyl group-containing polymerizable compound to obtain a modified acrylic resin molded gold.

Next, one embodiment of the present invention will be explained in more detail with reference to examples, but the present invention is not extended by the following embodiments unless it goes beyond the gist of the invention.

In the examples, the degree of surface energy reduction is shown by the measurement results of the contact angle of water on the resin surface.

In other words, the larger the contact angle of water, the smaller the wetting amount.

Indicates low surface energy. Use a goniometer (Kyowa contact gel meter 0A-D-1 type) for measurement ◎ Example acrylic resin (Mitsubishi Rayon product, Acrypella MD)
100 weight, C, F',, So, N (C8H,) in the mouth part
C,H4-0COCH=Of(,0.5 parts by weight and 2JItf for the above perfluoroalkyl group-containing monomer
Add benzoyl peroxide (BPO)'i from TJ and place a portion of the 6 mixture mixed in a tumbler mixer into a mold.
A disk 42 was prepared by melt molding at 200°C, 5 hours, and 50 kl/cm'', and the contact angle of water on its surface was measured, and the measurement results are shown in Table 1.

Comparative example 1 size 6 and 2 Cg of Example 1 J2801N (Cs Ht) C
tH40COCH=CI, and the contact angle of water on the surface of the disk obtained by the same treatment 1 as in Example 1 in the case of no addition of a polymerization initiator and in the case of no combination of a polymerization initiator, and the measurement results are as follows. are also listed in Table 1 as Comparative Examples 1 and 2. According to Table 1, the contact angle of Example 1 was significantly increased compared to Comparative Examples 1 and 2.

m1 table * C, F,, So, N (C6H7) Ct
El< 0COCH= M rat example 2 for C horse C,F,,5o2N (C,H,) C,)f40CO
C(CH,)=CH20,5y- and cumene peroxide (C
HPO) 5■ to 1,1,2-trichloro-1,2,2-
A disk was prepared under the same conditions as in Example 1 by immersing it in 50 ml of trifluoroethane and then evaporating the solvent, and the total contact angle of water was measured to be 98°.

Comparative Example 3 A disk was prepared in the same manner as in Example 2 except that no polymerization initiator was used, and the contact angle of water was measured to be 64.5°.

Example 3-11 Ca F: +y B Os N (CA Hy
)Ct 'H40COC1K = CFf! Disks with different amounts of addition and polymerization initiator were made under the same conditions as in Example 1, and the contact angle of water was measured for each disk, and σaJ fixed M! are shown in Table 2 as Examples 3 to 11.

Table 2 “C$FI? Boy N CCHH7)Ct H
4QCOCH=CH! Weight Jt% Comparative Examples 4 to 6 The same process as in Example 3 except that no polymerization initiator was included. Disks were prepared, and the water contact surface was measured for each disc, and the measurement results were Table 2 shows comparative examples 4 to 6.
Also listed as

Examples 12-15 Various perfluoroalkyl group-containing monomers were added to acrylic resins. When benzoyl peroxide was used as a polymerization initiator, the process was carried out in the same manner as in Example 1. When cumene peroxide 'fC was used, the process was carried out in the same manner as in Example 2 to produce a disk, and the contact angle of water was determined. Measurements were taken and the measurement results will be shown to the 3rd Sanada.

Comparative Example 7 A barfluoroalkyl group having a carbon number within the claimed range of the present invention was treated in the same manner as in Example S 1, and the contact angle of water with respect to the disk pressure obtained was 'kilT! The measurement results are also listed in Table 3 as Comparative Example 7.

Claims (1)

[Claims] fl) Adding and mixing a polymerizable compound containing a barfluoro-gastric alkyl group and a radical polymerization initiator to an acrylic resin, and then melt-molding f, an acrylic resin with characteristic surface properties modified. A method for producing a resin molded body. (2) A polymerizable compound containing a barfluoro-alkyl group represented by M has the general formula % (However, R in the formula is a fluoroalkyl group or perfluoroalkyl group having 3 to 20 carbon atoms. Rlp is an alkyl group having 1 to 5 carbon atoms, R4 is an alkylene group having 1220 carbon atoms, and R, R, is a hydrogen atom or a methyl group. (3) The manufacturing method according to claim (1), wherein the radical initiator indicated by # is composed of an organic peroxide or an azo compound. (4) The amount of the acrylic resin 100! % of the polymerizable compound containing a barfluorotetraalkyl group 't O,1~
5.0 parts by weight (PHR) and 0.4 to 5.0 parts by weight of the radical polymerization initiator to the perfluoroalkyl group-containing polymerizable compound K. Oli! t 5J km 7JI
JR matching claims (1), (2) and (3)
).