JPS5974111A - Method for producing fluorinated acrylic resin multistage polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to fluorinated acrylic resin multistage polymers. More specifically, the present invention relates to a fluorinated acrylic resin multi-stage polymer that does not easily undergo elongation failure in an applied strain test at room temperature and has excellent weather resistance, solvent resistance, and water and oil repellency.

Fluorinated acrylic resins, especially fluorinated alkyl methacrylate polymers, are used in optical materials that take advantage of their beautiful appearance, excellent transparency, and low refractive index.They are also water and oil repellent, making them useful as fiber treatment agents. Recently, it has been especially used as a treatment agent for antifouling treatment (SR treatment). However, since these lower fluorinated alkyl methacrylate homopolymers are hard and brittle, various studies have been made to impart elasticity to them when used for special purposes. As a method of imparting elasticity, higher fluorinated alkyl methacrylate (3,3,4,4,5,5,6
,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate・hereinafter 17FM
A) and methyl methacrylate or fluorinated alkyl methacrylate, polyvinylidene fluoride, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropene copolymer, vinylidene fluoride A method of blending an elastic polymer such as -hexafluoropropene-tetrafluoroethylene co-M 8 with polymethyl methacrylate or polyfluorinated alkyl methacrylate has been carried out. The former is a copolymer mainly composed of methacrylate (17FMA) with long-chain fluorinated alkyl groups, but the homopolymer of 17FMA is rubber-like at room temperature;
Since molding is difficult, it is copolymerized with methyl methacrylate or fluorinated alkyl methacrylate, which has a relatively high glass transition temperature, to improve processability and maintain a low refractive index. However, this method has drawbacks such as the high price of the higher fluorinated methacrylate, and because it is a homocopolymer, it does not have high elongation at room temperature.

In addition, in the latter method of blending an elastic polymer and methyl methacrylate, a rubber elastic body with a high fluorinated content is obtained.
Polymethyl methacrylate-1-f is a blend system of alkyl methacrylate and a vinylidene fluoride polymer with extremely good phase compatibility, which enables a wide range of blend components, and A transparent resin body with a low refractive index is obtained. However, since vinylidene fluoride polymers are crystalline polymers, their heat resistance behavior has been tracked to reveal that their crystallinity increases with heating, resulting in a decrease in the transparency of the polymer, which is a major drawback. Currently, it is used as a molding material such as injection molding material while retaining these defects. However, the heat resistance of these blended polymers is an extremely important factor when used as a film or sheet binding material or as a laminated material to other materials. Product value will drop significantly.

In view of the current situation, the present inventors conducted a detailed study on the structure of the polymer itself, and found that it has particularly high elongation.

As a result of intensive studies to obtain a polymer with excellent heat resistance and low refractive index, the present invention was achieved.

That is, the gist of the present invention is that the outer layer of the rubber layer made of a polymer mainly composed of fluorinated alkyl acrylate or fluorinated alkyl methacrylate with a glass transition temperature of O'C or lower has a glass transition temperature of 50°C or higher. This is a fluorinated acrylic resin multi-stage polymer characterized in that a resin layer is formed of a polymer whose main component is fluorinated argyl methacrylate.

The rubber layer in the multistage polymer of the present invention is fluorinated alkyl acrylate or fluorinated alkyl methacrylate (AI
) component and optionally a monomer (A2) having a double bond that can be copolymerized with (A1), a polyfunctional monomer (A, ),
Contains a graft cross-agent (A4) and has a glass transition temperature of 0°C
4J Fat M consists of a monomer (B2) having a double bond that can be copolymerized with fluorinated alkyl methacrylate (Bl) and optionally (B1), and has a glass transition temperature of 50°. The fluorinated acrylic resin multi-stage polymer of the present invention can be produced by coordinating a resin layer on the outer layer in the presence of the above-mentioned rubber layer polymer.

On the rubber layer? When rubber elasticity is particularly required, it is preferable to copolymerize a polyfunctional monomer (A). By copolymerizing a polyfunctional monomer (A3) into the rubber layer,
The resulting multistage polymer exhibits rubber elastic behavior due to the crosslinked rubber layer and has high elongation.

Furthermore, by copolymerizing the graft cross-agent (A4) in the rubber layer in order to perform a graft reaction with the resin layer, the resulting multistage polymer has excellent transparency and maintains high elongation. Therefore, the multi-cast polymer obtained by copolymerizing both the polyfunctional monomer (A) and the grafting agent (A4) as rubber layer components exhibits rubber elastic behavior due to the crosslinked rubber layer, Provide a multistage polymer with high elongation and good transparency.

The monomer (A2) having a double bond copolymerizable with fluorinated alkyl acrylate or fluorinated alkyl methacrylate (AI) as a rubber layer component is an important factor for varying the glass transition temperature, but it is not always ( A2) It is not necessary to copolymerize the components.

Also, as a resin layer component, fluorinated alkyl methacrylate)
Monomer (B2) having a double bond that can be copolymerized with (Bl)
) is also an important factor in changing the glass transition temperature; however, as a resin layer component, components (B and ) may be homopolymerized, and are not necessarily limited to copolymerization.

In order to obtain rubbery properties, unless the glass transition temperature is 0° C. or lower, rubber elasticity will not be exhibited at room temperature, and it is difficult to obtain high elongation. In addition, from the viewpoint of mechanical properties, it is difficult to obtain good processability in film forming, extrusion molding, injection molding, etc. unless the glass transition temperature is 50° C. or higher. In order to have both rubber elasticity and mechanical properties, the present invention uses a multi-stage polymer in which a resin layer is formed on the second layer of the rubber layer. ) and a resin layer component (Bl) having a glass transition temperature of 50°C or higher is preferably 95 to 25 parts by weight.The content of component A is preferably 5 to 75 parts by weight. 5
If the content of component A is less than 75 parts by weight, high elongation cannot be expected, and conversely, if the content of component A is more than 75 parts by weight, processability will decrease.

If the content of component A is 5 parts by weight or more and the multi-stage polymer structure is relatively small compared to component B, component B will undergo a glass transition even if it is a polymer with a relatively low glass transition temperature close to 50°C. If the temperature is 50°C or higher, workability and high elongation are good. Conversely, when the content of component A is 75 parts by weight or less and has a relatively large multi-stage polymer structure with respect to component B, component B has a glass transition temperature of 50 ° C. or higher,
Even higher glass transition temperatures tend to result in better processability and high elongation.

Rubber layer or resin layer in the present invention? As the constituent fluorinated alkyl acrylate and fluorinated alkyl memethacrylate, those represented by the basic structural formula 2 are used. Among them 2,2-difluoroethyl methacrylate (2FM).

2.2.2-1- Lifluoroethyl methacrylate (
3FM), 2.2,3.3-tetrafluoropropyl methacrylate (4FM), 2,2,
3,3.3-pentafluoroglovir methacrylate (
5FM).

2, 2.3.3.4.4-hexafluorobutyl methacrylate (6FM), 2,2,3,3,4.4
,5.5-octafluoropentyl methacrylate C8
FM).

1.1-ditrifluoromethyl-2,2,2-h trifluoroethyl methacrylate (9FM) + 2.2°3
, 3.4.4.5.5, 6.6.7.7-dozocafluorohebutyl methacrylate (12F M ), 3,
3,4,4,5,5゜6,6.7.7.8.8.9.9
, 10,1.0.10-hebutadecafluorodecanyltu tacrylate (17FM), and the above-mentioned acrylates having a fluorinated alkyl side chain can be used. Fluorinated acrylates and fluorinated methacrylates may have linear monobranched side chains and may be used alone or in combination, and the glass transition temperature is preferably for rubber layers or lower. In addition, monomers (A2) and (B2) having 2 copolymerizable double bonds include lower alkyl (meth)acrylate, lower alkoxy (meth)acrylin-tocyanoethyl (meth)acrylate, acrylamide, acrylic acid, metaglyl. Acrylic monomers such as acids are preferred.

In addition, styrene, alkyl-substituted styrene, acrylonitrile, methacrylate trile, etc. may also be copolymerized and used. Here, the amount of monomers (A2) and (B2) having copolymerizable double bonds is a factor that can greatly change the glass transition temperature and also a factor that can change the refractive index. In order to maintain the properties of the alkyl (meth)acrylate, it is preferable to use as little as possible.

The polyfunctional monomer (A
, ) include alkylene glycol dimethacrylates such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate and butylene glycol dimethacrylate.

Nopolyvinylbenzenes such as polyvinylbenzene, divinylbenzene/trivinylbenzene, alkylene glycol diacrylate, etc. can also be used as the polyfunctional monomer (A3).

These polyfunctional monomers effectively act on the crosslinking of the rubber layer itself, but do not act on the interlayer bonding with the resin layer. The polyfunctional monomer (A3) can give a fairly stable multi-stage polymer even if it is not used at all as long as the grafting cross-agent (A4) is present, but it can be used in cases where hot strength elongation is strictly required. Any amount may be used depending on the purpose of addition, but the range of dosage is as follows: Rubber layer component (A) 100 Weight As a specific example of the grafting agent (A4), copolymerizable α
, allyl esters, methallyl esters or crotyl esters of β-unsaturated carboxylic acids or dicarboxylic acids, preferably allyl esters of acrylic acid, methacrylic acid, manic acid and fumaric acid. In particular, allyl metatarylate has excellent effects as a graft crossover agent. In addition, triallyl cyanurate, triallyl in cyanurate, etc. are also effective as graft cross-agents. In such a graft cross-agent, the conjugated unsaturated bond of the ester reacts faster than the allyl group, methallyl group or crotyl group, and chemically bonds to the ester. During this time, allyl group.

A substantial portion of the [meta]nor group or crotyl group acts effectively in the next layer of polymer to provide a graft bond between two adjacent layers. The amount of the grafting agent used is preferably within 10 parts by weight per 100 N of rubber layer component (A). More preferably, the amount is in the range of 0.1 to 5 parts by weight per 100 parts by weight of the rubber layer component (A).

If necessary, antioxidants, ultraviolet absorbers, fillers, pigments, etc. can be added to the resin composition obtained by mixing the multistage polymer of the present invention and a specific thermoplastic resin. Furthermore, the fluorinated acrylic resin multistage polymer of the present invention can also be used as a sheath material for plastic optical fibers.

Hereinafter, the present invention will be specifically explained with reference to Examples. In Examples and Comparative Examples, parts indicate parts by weight, and parts by weight indicate parts by weight. In addition, the glass 7 of each polymer layer used in Examples and Comparative Examples
The transition temperature (Tp) is determined, for example, from the Polymer Handbook (J
ohn Wl 11ey & 5ons Publisher) K
It is calculated from the stated value of T/ using the commonly known Fox formula.

The tear strength was measured according to JIS P-8116 using the Elmendorf method with a cutting depth of 2IIIm.

Other performance evaluations were performed using the following methods.

Film sheet bending whitening film sheet) '2180° Shows the whitening state when folded.

The evaluation results are displayed as follows.

◎ Almost no whitening ○ No whitening △ Whitening observed × Whitening × Folding (brittle) Sheet plate transparency The transparency of the above extruded sheet was measured using an integrating sphere type haze meter (according to ASTM D1003-61). )
.

The advancing contact angle (θ) of the contact angle versus water was determined and used as an evaluation of water repellency.

A Kyowa contact angle meter model CA-P was used for convenience.

Processability Nutland state made by 25φ extruder show.

× Bad △ Moderate ○ Good Example 1 250 parts of ion-exchanged water and potassium perfluoroalkyl sulfonate (Megafac F
-110 (manufactured by Dainippon Ink Chemical), 0.05 part of sodium formaldehyde sulfoxylate, and after stirring under nitrogen, 50 parts of 2,2゜2-trifluoroethyl acrylate, 5 parts of 1,3-butylene glycol dimethacrylate. 1 part allyl methacrylate and 0.4 part cumene hydroperoxide. 7
After raising the temperature to 0° C., the reaction was continued for 60 minutes to complete polymerization of the rubber layer. 2.2.2-trifluoroethyl methacrylate) 50i, n-octylmercaptan 0.5
1 part, and a mixture consisting of 0.4 parts of Kume/hydroperoxide was added dropwise over 120 minutes for polymerization.

The obtained polymer was in a water-dispersed latex state, and the polymerization conversion rate was 99%. The latex particle size was 850A.

100 parts of the polymer emulsion thus obtained was salted out using 5 parts of calcium chloride, washed, dried, and extruded. The residual amount of calcium in the final polymer composition was 200 ppm.

The obtained polymer was press-molded at 220°C to a thickness of 50 μm.
A film of m was prepared. The refractive index was +, 14-21 Note 44, and the advancing contact angle with water was 79°. Although the bendability was good, there was some whitening. When the behavior was measured, the elastic loss peak of E'(dyr/Cm2) showed a gentle dispersion from 40 to 60°C.

Tan δ had a peak at 65°C. The light transmittance is 90%, the haze is 3%, and the tensile elongation at break is 1.
It was 5chi.

Examples 2 to 4 Polymerization was carried out in the same manner as in Example 1, except that other fluorinated alkyl acrylate was used in place of 2,2.2-) fluoroethyl acrylate in Example 1. A sample was prepared and evaluated in the same manner as in Example 1. The results were as shown in Table 1.

Comparative Example 1 In a polymerization container equipped with a cooler, 250 parts of ion-exchanged water and potassium perfluoroalkylsulfonate (Megafasoku F
-1 part (manufactured by Dainippon Ink Chemical), 0.05 part of sodium formaldehyde sulfoxylate, and after stirring under nitrogen, 50 parts of 2,2゜2-trifluoroethyl acrylate, 1.3-butylene glycol di A mixture consisting of 5 parts of methacrylate, 1 part of allyl methacrylate and 0.4 part of cumene hydroperoxide was charged.

After raising the temperature to 70°C, the reaction was continued for 60 minutes to complete polymerization of the rubber layer. Subsequently, 50 parts of 2.2.2-trifluoroethyl methacrylate and 0.2 parts of n-octyl mercaptan were added.
Polymerization was carried out by adding dropwise over a period of 120 minutes a mixture consisting of 5 parts of DAM and 0.4 parts of DAME/NOIDROBA-OXIDE.

The obtained polymer was in a water-dispersed latex state, and the polymerization conversion rate was 98%. The latex particle size was 900A.

5 parts of calcium chloride was used to salt out 100 parts of the polymer emulsion thus obtained, washed, dried, and extruded.

The obtained polymer was press-molded at 220°C to a thickness of 50 mm.
A μm film was created. The flexion snoring rate was 1.4203. The contact angle was 79°.

It was brittle and broke easily. The E' peak was relatively sharp and showed 92° CY. Light transmittance & S93%
, haze was 2%, and tensile elongation at break was 3%.

Examples 5 to 9, Comparative Examples 2 to 3 The polymer composition in Example 1 is shown in Table 1 7-5
Polymerization was carried out in the same manner as in Example 1 except that the following was changed, and a film was prepared and evaluated in the same manner. The results are summarized in Table 1.

In Comparative Example 4, the glass transition temperature of the rubber layer was set to 0° C. or higher, but the obtained polymer was inferior in elongation at break and in properties of precipitation.

In Comparative Example 5, the glass transition temperature of the resin layer was set to 50° C. or lower, but the processability of the film and sheet was poor.

Table 1” BD snee71 90 19011.
2.4FA 5゜'3FM S total IBD
51 1. −2゜′,. □ 9゜□ ”/ 318FA 5013FM 501
1BD s, , -41
9011 Seal/44 Fukan FM Door-31' 90 AMA I BD 5. -55 9
0:92AMA]'''11pa'°゛°°°°“ ”” 90 90
'931 BD 51...2↑3FM 5013FM"5011 - -
1 □90 j 90 19
3 No. 1 3'3 FM100 Le-------□ 1 '9019310
0- 1:3.17911,421f △ l 15 □○
i: "□-・-i l l'3. .35::01 518011.395101 1 1'1--.1-1., ,, , l-,,,,,
,,112,7911,4201X l 310 □
□ ,: ′・″ツ一１′、□′１０′□ □ ' i ' 21o1 2.7□1.421上 1 1 j□

Claims (1)

[Claims] The outer layer of the rubber layer is made of a polymer mainly composed of fluorinated alkyl acrylate or fluorinated alkyl methacrylate with a glass transition temperature of 0°C or lower, and has a glass transition temperature of 50°C.
A fluorinated acrylic resin multi-stage polymer comprising a resin layer formed of a polymer containing the above-mentioned fluorinated alkyl methacrylate ()Y as a main component.