JPS59129208A - Fluoroalkyl methacrylate resin - Google Patents

Abstract

PURPOSE:The titled resin excellent in heat-decomposition resistance, adhesiveness, transparency, etc., and suitable for use in optical materials, etc., obtained by copolymerizing a monomer mixture comprising a fluoroalkyl methacrylate and an ethylenically unsaturated dicarboxylic acid monoester. CONSTITUTION:A mixture is formed from (A) 50-99.95pts.wt. fluoroalkyl methacrylate monomer of formula I or II (wherein X is H or F, m is 1-5, and n is 1-10), e.g., 2,2-difluoroethyl methacrylate, (B) 0-30pts.wt. vinyl monomer cpolymerizable with component A, e.g., methyl methacrylte or butyl methacrylate, and (C) 0.05-20pts.wt. ethylenically unsaturated dicarboxylic acid monoester (e.g., monobutyl intaconate or monooctyl itaconate). The formed monomer mixture is copolymerized to obtain the purpose fluoroalkyl methacrylate resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fluorinated alkyl methacrylate thread and resin which is excellent in heat decomposition resistance, layer adhesion, carbon water oil repellency, low moisture absorption and permeability.

To explain in more detail, the invention is to prevent thermal decomposition reactions based on decomposition during heat molding during press molding or injection molding, and to have good adhesion to other resin polymers, glass, and metal surfaces. It is a fluorinated alkyl methacrylate that has excellent properties such as excellent water repellency, low hygroscopicity, and visibility.

Heptafluorinated alkyl methacrylate thread tree 11 of the present invention;-r
This material is used as a weather-resistant film and a sheath material for optical fibers.

Fluorinated acrylic resins, especially fluorinated alkyl methacrylate resins, are used in optical materials that take advantage of their beautiful appearance, superior clarity, and low refractive index. Also,
Since it is water and oil repellent, it is also used as a fiber treatment material, and recently G! S R (5 oil release
) Used as a processing agent.

In this way, it is functionally applied as an industrial material in special areas7.
'However, at present it still contains fluorine.
It is said to be the lily of plastics because m is the recitation value, and when compared with general-purpose resins, polymerization methods and molding methods have not yet been able to fully establish the branch number.

For example, when a fluorinated acrylic resin or a mixture of it and a general-purpose resin is subjected to high-temperature thermoforming, problems such as jetting and generation of silver occur, resulting in poor quality of the processed product. For this reason, these fluorinated acrylic resins are forced to be processed at low temperatures and in low crosstalk conditions.
At present, problems remain in formability. Furthermore, after forming a regular fluorinated acrylic resin into a film, when laminating it with a general-purpose resin, metal, or glass plate, the water-repellent, oil-repellent properties are Because of this, the contact strength between the two is low, resulting in easy peeling.

For example, as a film sheet laminating material or a fiber processing agent, it is not suitable for G-go since it requires a certain level of wearability.

In view of this current situation, the present inventors have conducted extensive research aimed at improving the formability based on the above-mentioned thermal decomposition, as well as improving the adhesion properties. We have demonstrated that a fluorinated alkyl methacrylate thread resin obtained by copolymerizing a polymer with an ethylenically unsaturated dicarboxylic acid monoester in a specific ratio exhibits remarkable effects in preventing the above-mentioned thermal decomposition and improving layer adhesion. Heading, we arrived at the present invention.

'f 7f The present invention is a fluorinated alkyl methacrylate, 1'-Ljk body) so ~9 993 Wheelchair t11
≦, copolymerized with a vinyl monomer skewer) 0
~30 parts by weight, ethylenically unsaturated dicarboxylic acid monoester monomer (C) 0.0! It is a fluorinated alkyl methacrylate resin obtained by copolymerizing a monomer mixture consisting of 20 electromagnetic parts.

Methacrylic T! 11, when the resin of the present invention is laminated with a film on a substrate such as polystyrene, polycarbonate, quartz, multi-component optical glass, iron, aluminum plate, etc., good adhesion and thermal properties can be achieved. It provides heat decomposition resistance during processing.

Here, ethylenically unsaturated dicarboxylic acid monoester t￥
The L-mer (C) has the ability to reduce the water and oil repellency of the fluorinated alkyl methacrylate vehicle, which is the main component. is satisfied.Especially when it comes to the contact with λi, thermoplastic yuzu resin is used as a general-use co-press v-1 product with the above-mentioned lacquered acrylic yarn resin, and quartz multi-component glass and aluminum plate are used as rI) Kenoro Court 13K ItC-i) Determined by 4. 111"
Famous persimmons for heat use; in the case of contact with metal, static property on the surface of molten material, G in contact with quartz, glass, iron, aluminum & etc. in the after bath.
This shows the adhesion of 591 bodies and the amount of bath melt. In addition, I would like to add that 1 bottle of ethylenic dicarbonate, which is the main component of these products, 1 bottle of ester, 1 bottle of T-I Co., Ltd. (C
It also plays a role in preventing the thermal decomposition of the fluorinated argylmethacrylate polymer, which is the main component of Moon J, during melting in a high-temperature bath.

It should be noted that the solution properties of the fluorinated alkyl methacrylate monomer are that when compared with the alkyl methacrylate monomer that is compatible with this monomer, it retains a water-repellent fluorinated alkyl monofunctional group as a vinyl side beam. However, 7b has poor solubility in baths having strong polar functional groups.

For example, itacon glaze, which is caused by ethylenic non-candy and dicarbonate cough, is not easily resolved at room temperature. However, using these ethylenically unattached dicarboxylic monoester monomers (e.g., itacon, methyl, monobutyl, monohexyl, monooctyl, futai, etc.) improves the yukano properties and It exhibits good copolymerizability with the component fluorinated alkyl methacrylate and the vinyl monomer that can be co-polymerized with the TL.0 Thermal decomposition is essentially the radical decomposition of the main term by the fluorinated alkyl methacrylate as the main component. It is based on polymerization. In particular, in the case of polymers consisting of frozen units of monomers having fluorinated alkyl groups in their side chains, the depolymerization activation energy decreases due to the electron-withdrawing effect of the fluorinated alkyl group side hooks. This results in easier radical depolymerization than alkyl methacrylate which undergoes 1+jt. In order to inhibit this radical depolymerization, it is known that it is effective in practical handling to add a radical trapping reagent such as hydroquinones, hindered phenols, or mercaptans to the resin-based composite (see I). However, such methods only reduce the rate of progress of depolymerization, but do not actively prevent shellfish disintegration.

10,000 As in the present invention, a free carboxylic acid is retained at the α position,
The behavior of the thermal component i9'6 of the fluorinated alkyl methacrylate thread bij co-combination when the other carbone is esterified to increase the compatibility to the fluorinated alkyl methacrylate main component 14'-i-j'cIN is as follows. Disassociation prevention can be inserted based on the following ``1i definition.''

In the polymer chain, the carboxylic acid in the monomer having a side carboxylic acid functional group at the α-position is the 'JJB g4 in the fluorinated argyl methacrylate monomer after the preamble
VC to combine with the ester carbonyl group of hydrogen ^ζh,
The depolymerized terminal radical during radical termination is stabilized,
Moreover, it is estimated that the reinforcement of the +N k combination energy by the lateral pedicle connection substantially prevents the 1-il combination and 1-noro, resulting in the effect of inhibiting the % 'A's combination. Become.

In order to create such a hydrogen bond, '1JJf in the ethylenically unsaturated dicarbonate monoester group:
It is preferable that the free carboxylic acid be at the alpha position, which is directly connected to the main chain.

In this book, it is a fluorinated alkyl methacrylate single body), for example, a general formula or a general formula CH2=C-C-0-C-(CF2) X11 0 0F3 (in the formula, is H or Fsm is /~left=h, n is 1 to 1
Indicates an integer of 0. ) is used,
Specific examples include 21.2-difluoroethyl methacrylate), 2. ．． 2.2-trifluoroethyl methacrylate, 2. :1.3.3-tetrafluoropropyl methacrylate, 2,2°3.3.3-pentafluoropropyl methacrylate, 2. ．． 2, 3. J, Ri, Darhexafluorobutyl methacrylate, 2,1. ,j,,3.
ll, II, jS:, j-octafluoropentyl methacrylate, /.

l-di(trifluoromethyl)-1 item2. ．． 2-) Lifluoroethyl methacrylate, 2,2. ．． 3゜3, g,
G, S, Shio, Otsu, Otsu, 7,7-dotecafluorobentyl methacrylate, 3. ．． 3. 'I Mamoru...!';.

A, A, '), '/, g, g, 9, 9, 10, 10. /
Examples include θ-hetafluorofluorinyl methacrylate.

In the present invention, examples of vinyl shosha that can be combined with fluorinated alkyl methacrylate (monofluorinated methacrylate) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, lauryl methacrylate, and nonyl methacrylate. , methyl acrylate, butyl acrylate, conityl-hexyl acrylate, styrene, α-methylstyrene and the like. However, monophosphorous methacrylates are preferred from the viewpoint of coagulation properties.

Monomers with a carboxylic acid functional group in the alpha position or monoesters of ethylenically unsaturated dicarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, glutaconic acid, 3-methyl -Glutaconic acid, mucontan, dihydromuconic acid, methylene malonic acid, citraconic acid, mesaconic acid, methylene glutaric acid, etc., and examples of the monoester part (7) alcohol include methanol, ethanol, n-propyl, Common alcohols such as isopropanol, butanol, pentanol, hexanol, and octyl alcohol can be used.

Also general formula %formula%) or general formula CF3 X-(CF,)-C-OH C.F.

(In the formula, m is an integer of /-, 1, n is an integer of / to 10, and X is H or FF) can also be used.

The fluorinated alkyl methacrylate yarn resin of the present invention can also be usefully used as a plastic optical transmission fiber made of polymethyl methacrylate, polystyrene, etc., or as a sheath material for a YC transmission fiber made of multicomponent glass, quartz glass, etc.

The present invention will be specifically explained below using Examples.

In the Examples and Comparative Examples, all parts indicate part of the seedlings, and all percentages indicate weight %.

Furthermore, in the previous Examples and Comparative Examples, heat resistance and hard adhesion were evaluated by the following methods.

(1) Evaluation of dense layer property Fluorinated alkyl methacrylate yarn h fat E N is created by bulk polymerization and crushed with a crusher to obtain / g
OC,! After obtaining a film with a thickness of /3Qμ by hot pressing under the conditions of / o o kglcrl for r minutes, a substrate (plastic plate, aluminum plate, iron plate, glass plate, etc.)
This film la overlap 1.230c, 10 seconds,! rk
A laminate was obtained by pressure bonding under the conditions of glcrl. For the film laminate plate obtained in this way, JIS
A: The adhesion was evaluated as 6!1' by the board test judgment using Da00, and judged based on the following criteria. is thin and smooth on both sides,
It will not peel off at the intersection of the cut and the 7th eye of the square.

g. There is a slight flake at the intersection of the cuts, and there is no blemish in the eyes of the square. The area of the defective part is 5-is% of the total square surface.The width of the peeling due to the cut is wide.The width of the defective part is 1 to 35% of the total square area. The area of the widely defective part is 35% to AS% of the total square area. JISZ-ggO1R rating /A
Separate into 32 pieces, 2S
Beret l by φ bent type presser machine (Osaka Seiki Belly)
1 JEf, L r:.

The thermal decomposition resistance test was carried out by heating the core in a gear oven (manufactured by Tawai Seisakusho) in a strained atmosphere of core θC. /type) in a nitrogen atmosphere with constant temperature rise heating (/QC/min).
It was evaluated by the hospital.

Example 1 212,-monotrifluoroethyl methacrylate 9 Q
parts, 3 parts of methyl methacrylate, 2 parts of monooctyl itaconate, azobisbutyronitrile θ0! r part, n-
After mixing octyl mercaptan θ/WS, 2
The autoclave for bulk polymerization described in No. 1 was charged and sealed after repeated degassing and purification. After polymerization by immersing in qoC warm water for 70 hours, the internal pressure became '01cg7Cm2 gauge pressure, and after further heating at qoC for 3 hours, the nail platform exothermic peak was completed and the polymerization was completed. The polymerization conversion rate was 99%. The refractive index of the polymer < n, 25 ) is / tick left (
(measured with an Atsube refractometer).

This main assembly is crushed by a crusher and JIS-Z
-ggO/Standard/A Me”) C3- Hass, 3.1
After separation into mesh parts, a film with a thickness of /SOμ was prepared and the dense layer L was evaluated as h. In addition, a strand pellet produced by a pressing machine was used as a sample for heat decomposition resistance testing.

Adhesion to polymethyl methacrylate plate (Mitsubishi Rayon Acrylite@)) is 10, to polystyrene (Dow Chemical Stylon ■) to 1, to polycarbonate (Teijin Kasei Panlite), IQ, hardness The rating was B for the glass plate, A for the steel plate, and A for the aluminum plate.

Heat decomposition resistance 270C gear oven heating loss for 30 minutes (
-%), 60 minutes (5%), and 120 minutes (72%). Thermal analysis results are 39! at a constant temperature increase rate of 1OCZ minute! 'I
: (!; 0%) - 11F (11F) with good sealability and heat decomposition resistance.

Examples - Copolymer compositions were varied as shown in Table 1, and copolymer copolymers were prepared and evaluated in the same manner as in Examples. The evaluation results are summarized in Tables 1 and 2.

Copolymerizability, adhesiveness, and heat decomposition resistance were all good.

Comparative Example: Manufactured and evaluated according to Example except for the ethylenically unsaturated dicarboxylic alcohol/ester monomer as the KN component. The results are shown in Tables 1 and 2.

Comparison fA, 2 According to Example/Itaconic acid was used as adhesive component. Itaconic acid G could not be evaluated because it was not understood to be a single mixed substance with the simple combined composition described in the first article.

Example g The polymer obtained in Example 2 was used as a cladding component, and the mata polymethyl methacrylate was used as a stone component.
It was wound up at a speed of 7 m1n. The obtained filament has a diameter of 0.3 mm, a core diameter of 0, 'i' 7
The cross section of m was concentric and the surface of the filament was smooth.

The optical transmission loss of this filament &';l 3/3
dB/km and excellent 21. T: It was something. Furthermore, the diameter of this filament,! Even when I wrapped it around my friend's mandrel and magnified it under a microscope, no cracks were found in the cladding.

Claims (1)

[Claims] / Fluorinated alkyl methacrylate monomer (A) SO~
vinyl monomer (qq, qs vehicle weight unit,
B) 0 to 30 parts by weight, ethylenically unsaturated dicarboxylic acid monoester monomer (C) A monomer mixture consisting of O, O, and 20 parts is copolymerized to form N7 tufted alkyl methacrylate. Thread resin. fluorinated alkyl methacrylate monomer) or general formula 0 CF3 (wherein, 3. The fluorinated alkyl methacrylate persimmon fat according to claim 1, which is a compound represented by the following: The fluorinated alkyl methacrylate thread persimmon fat described in Section 1.