JPS5998116A - Multi-stage polymer of fluorinated acrylic resin - Google Patents

Abstract

PURPOSE:To provide a fluorinated acrylic resin multi-stage polymer having high elongation, excellent heat resistance and low refractive index, etc., and suitable as a stainproofing agent, etc., by laminating three or more layers of fluorinated alkyl (meth)acrylates having different glass transition temperature from each other. CONSTITUTION:The objective multi-stage polymer is prepared by using (A) a rubbery layer composed of a polymer composed mainly of a fluorinated alkyl (meth)acrylate having a glass transition temperature of <=0 deg.C as the inner layer, (B) a resin layer composed of a polymer composed mainly of a fluorinated alkyl methacrylate having a glass transition temperature of >=50 deg.C as the outer layer, and (C) one or more intermediate layers composed of a polymer having a glass transition temperature (Tg) higher than that of the rubbery layer (A) and lower than that of the resin layer (B). The fluorinated alkyl (meth)acrylate is preferably the compound of formula I (m is 1-5; n is 1-10; X is F or H; Z is H or CH3) or formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to fluorinated acrylic resin multistage polymers. In addition, the present invention is suitable for VC, which is applied at room temperature and does not easily cause elongation failure in licking and texturing, and has weather resistance, bath agent resistance, water and oil repellency VC, and a multi-layered fluorinated acrylic resin that can be beaten. A flash of fusion.

Fluorinated acrylic resins, especially heptafluorinated alkyl methacrylate yarn polymers, are used in optical materials that take advantage of their warp-resistant appearance, excellent swirling properties, and low refractive index. Due to its oily nature, it has recently been used as a fiber treatment agent and as an antifouling treatment agent (βR treatment).However, these polymers are hard and brittle when combined with lower fluorinated alkyl methacrylate alone. Therefore, when using it for special purposes, it is desirable to give it zero elasticity, and various studies have been carried out so far.As a method of imparting elasticity, grade 7 alkyl methacrylate (3
,,j,da,lI,j,j.

6.6. ? ,'),II,It,9,9,10,10,
10-hebutadecafluorodecyl methacrylate or less l
A method of making a copolymer with methyl methacrylate (referred to as FMA), polyvinylidene fluoride, vinylidene fluoride-tetrafluoroethylene copolymer, and vinylidene fluoride-hexafluoride Fluoropropyl copolymer, vinylidene fluoride-hexafluoropropyl alcohol Ai
Methods such as blending the polymer with polymethyl methacrylate or polyfluorinated alkyl methacrylate have been carried out. 1J11 is a combination of methacrylate (/7FMA) with a long-necked fufluorinated alkyl group as the main component; Because it is a female, glass rolling 4!!, methyl methacrylate material has a relatively high humidity, and together with fluorinated alkyl methacrylate ('J4), it improves the processing life and maintains a low refractive index. However, this method has drawbacks such as the fact that higher fluorinated methacrylates are currently available at market prices) and that it cannot achieve high elongation at low humidity because it is a simple copolymer.

In addition, in the latter method of blending the sterile kite combination with methyl methacrylate, etc., a rubber elastic body with a fluorination degree of It is a blended yarn with vinylidene fluoride yarn (combined) that has a compatible bathing property, making it possible to have a wide range of blending components and obtain a transparent resin body with a low refractive index. Since is a crystal-prone molecule, tracing its heat-resistant behavior shows that the degree of crystallinity increases with heating, and as a result,
The rectangular shape 1 has a major drawback in that its transparency is reduced. Currently, 61 is used as a molding material such as injection molding material while retaining these defects. However, the heat resistance of these blended yarn polymers is an important factor when used alone as a film or sheet or as a laminated material for a phase. If whitening occurs due to oxidation,
Product value GL drops significantly.

The present invention takes into consideration the current situation, and the Wtm of the polymer itself.
In order to obtain a pure composite with excellent properties such as 1% elongation, heat resistance, and low refractive index, the present invention was developed as a result of a detailed study of Reached.

That is, the gist of the present invention is that a fluorinated alkyl acrylate material having a glass transition temperature of OC or less has an inner layer of rubber IvJ (A) made of a polymer containing fluorinated alkyl methacrylate as a main component, and has a glass transition temperature of 1A. S.O.
Resin rw LBJ made of a polymer mainly composed of aluminum fluoride and kyl methacrylate of c or more is used as an outer layer, and a glass transition swell (Tg) of 1 degree is used as an outer layer between rubber)・i (AI and resin layer IB). Wither than the Tg of the layer [fat layer Tg
Fluorinated acrylic in which more than one intermediate layer (tC) consisting of lower 7i7 combinations is formed is also a "fatty stage polymer".

Rubber layer i in the multistage polymer of the present invention (Al is fluorinated alkyl acrylate or fluorinated algyl methacrylate) A monomer having a double bond copolymerizable with component (A,) and optionally (A,). 111 body (A2), a polyfunctional paper body (A, ), and a grafting cross-agent (A4), the resin layer (B) is a polymer having a glass transition temperature of OC or less. ) can be copolymerized with (B,) and optionally (B,).
f, body [B2] is composed of a polymer having a glass transition humidity of 500 or more.

Moreover, the rubber layer tAJ and the resin layer tB of the multi-stage true combination of the present invention
The layer 1cJ formed between the TL and IL) layers 1c and fluorinated alkyl acrylate or fluorinated algyl methacrylate CC,) and optionally (C,) together with the two bonds that can be combined with each other. The glass transition temperature (hereinafter referred to as Tg
The rubber layer) is made of a polymer whose Tg is lower than α) and the tree layer (B) is lower than α.

The Tg of each helmet is from the inner side to the outer side.

It is preferable to increase the middle 1uj layer (cJ/price drop 1 so (B) and single i + a. In the middle: ';'j (C) or when there are two or more layers, Tg is the rubber layer (from AJ to 11 Ej Iso t
It is preferable to uniformly add up to BJ.

Fluorinated alkyl acrylate or fluorinated argyl methacrylate (A,
), (C,) and a single captive body (A2), (C2) with a visible double bond in the chassis are important factors for varying Tg, or are they not necessarily (A2)1(C2)? It is not safe to copolymerize the components.

In addition, as a pine resin component, the monophenol (B2), which has a double Mh combination that can be copolymerized with fluorinated argyl methacrylate (B), is also an important factor for varying Tg. As a layer component, the component (B) may be homopolymerized, and is not necessarily limited to copolymerization.

In order to carry out the graft reaction with the intermediate layer tC1 and the oil layer tBI, the graft cross-agents (A, , C,) are added to the rubber layer tAl and the intermediate layer tcJ. It is preferable that both be combined. By copolymerizing these graft cross-agents, a multi-stage k-aggregate cross-linked rubber 1ρ exhibits rubber elastic suspension. The result is a laminate that has good properties and maintains high elongation.

Furthermore, in addition to the graft cross-agent, the rubber layer components include
By copolymerizing the functional monophosphor (A3), the resulting multistage polymer exhibits rubber elasticity and grafting effects,
It has high elongation and good transparency.

In order to obtain rubbery properties, unless Tg is θC or less, 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 such as film molding, extrusion molding, and injection coloring unless Tg is 500 or more. The content ratio of each layer is as follows: rubber layer (A) 5~j5, middle layer, te10, 5~9OdLM, row b, ・)lir ll1r Iso Preferably. Rubber I? The content i+L of ritAJ!
This is because if the amount is less than 75 parts by weight, the elongation of the multi-stage claw joint bar cannot be expected, and conversely, if the IM content of the rubber layer tAl is more than 75 parts by weight, the IJIJ workability will decrease.

The content of the rubber layer tAl is greater than or equal to S Tsumedento, and the content of the resin layer (B
), when the multi-stage electric combination has a relatively small amount of heat (Bl has good workability and high elongation even at a relatively low Tg as long as the Tg is above soC). If α has a multi-stage copolymer Sakaki structure in which the content of Comb I+Nia (A) is less than or equal to qs and is relatively larger than the resin layer tB), the resin layer tBJ has a Tg of 500.
As mentioned above, the content of the intermediate layer TCL is preferably S to 90 parts by weight, and more preferably 20 parts by weight. It is preferable that the vehicle volume be in the range of ~60 vehicles. Although it is generally difficult to describe its characteristics 2 due to the balance between the rubber layer tA) and the resin layer tB), we will show you the important role it plays in the stress whitening resistance during film and sheet molding of multi-stage copolymers. The stress whitening property is the same as above in the direction of the middle layer tel.

In the present invention, as the fluorinated alkyl acrylate and fluorinated algyl methacrylate constituting the rubber layer, intermediate IW, and resin layer, those shown in the basic formula (%) are used. Among them, the methacrylate is λ, 2-difluoroethyl methacrylate) (
2FM)1.2. ．． 2. Coated trifluoroethyl methacrylate (?FM), 2+2+J+3-tetrafluoropropyl methacrylate (Hiro FM), Ko, Yu,...
? ,,7. ．． ? -pentafluoropropyl methacrylate (,5-FM), co, coIJIj, 4', +-hexafluorobutyl methacrylate (AFM), co,
,I,3,3.4','I,j,3-octafluoropentylmethacryle-) (KFM),/,/-di(trifluoromethyl)-2,co-trifluoroethylmethacryle~ ) (9FM)1.2,2. J, 3. '1. II
, it, 3. A, A,'),? -dodecafluoro-p-butyl methacrylate) (/, 2FM), 3131 Hiro 1"
+ 5131'l 61? l'Ig
l Kl 9 + 9110. /θ-hebutadecafluorodecanyl methacrylate (/7FM), etc., and as the acrylate, those on the fluorinated alkyl side i can be used.

In addition, when using a rubber layer, an alkyl fluoride (in the case of methacrylate, either a linear or branched side chain may be used, and it may be used alone or in combination, and the lower the Tg is, the better). Monomer (A,) + having a heavy bond
(B2) and (C2) are acrylic spinning wheels such as lower alkyl (meth)acrylate, lower alkoxy (meth)acrylate, cyanoethyl (meth)acrylate, acrylamide, acrylic acid, methacrylic acid, etc.
Body is preferred. In addition, styrene, alkyl styrene, acrylonitrile, methacrylate trile, etc. can also be copolymerized and used. Here, the single support (A2), (82) + (C2) component I4i having a copolymerizable double bond is a factor that can greatly change Tg, and
However, in order to maintain the properties of the fluorinated alkyl (meth)acrylate, it is preferable to use as little as possible.

Polyfunctional monomer (A) used as a rubber layer polymer component
, ) include alkylene glycol dimethacrylates such as ethylene glycol dimethacrylate, 7,3-butylene glycol dimethacrylate, 4Z-butylene glycol dimethacrylate, and propylene glycol dimethacrylate.

Further, polyvinylbenzenes such as divinylbenzene and trivinylbenzene, algylene glycol diacrylate, etc. can also be used as the polyvinylbenzene (A). The polyfunctional ML material can also be used in the intermediate layer, and it acts effectively on the layer itself (vW) in which it is included, and does not affect the bonding between other layers or layers. .

Even if no polyfunctional monomer is used, as long as the grafting agent is present, it will give a fairly stable multistage copolymer;
It is optionally used depending on the purpose of adding it, such as when hot elongation is strictly required, but it has a rubber layer and an intermediate layer.
It is preferable that the range of the amount used is within 10 parts per 100 parts of the layer component.

10,000, as a graft cross-agent, copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid allyl ester;
Mention may be made of methallyl esters or crotyl esters, preferably allyl esters of acrylic acid, methacrylic acid, maleic acid and fumaric acid, with allyl methacrylate showing particularly excellent effects. In addition, triallyl cyanurate, triallyl isocyanurate, etc. are also effective as grafting cross-agents.

Such grafting cross-agents are mainly chemically bonded by the conjugated unsaturated bond of the ester reacting faster than the allyl group, methallyl group or crotyl group. During this time, a substantial portion of the allyl group, methallyl group, or T-crotyl group acts effectively in the next layer of polymer to provide a graft bond between two adjacent layers. The companies using the grafting agent are rubber layer component tAJ and intermediate layer component TCL.
It is preferable to use within the range of 10 IQ per 100 parts by weight. More preferably, the range is 0.0/~S.

An antioxidant, an ultraviolet V absorber, a filler, a pigment, etc. can be added to the sensin composition prepared by mixing the multistage polymer of the present invention and a specific rapidly turning plastic resin, if necessary. Also,
The fluorinated acrylic resin multi-stage wheel assembly of this promotion is made of plastic and quartz optical 'njl', i+Q (can also be used as a v-axis material).Hereinafter, this invention will be specifically explained with reference to examples. In Examples and Comparative Examples (/J part indicates parts by weight, % indicates sub-mouse %. Also, each main body combined layer σ used in Examples and Comparative Examples
For example, the glass transition temperature (Tg) can be found in the Polymer Handbook (published by John Willey & 3ons Publishers).
F, which is usually known from the 'fgOJ value listed in
It was calculated using the OXO formula. In addition, in the case of a polymer not described in the above-mentioned literature, the one determined from the DSC (differential thermal measurement value) measurement value was used. Furthermore, the total light transmittance of the film sheet in each example is ASTM D10θ3.
-61 Measured using an integrating sphere haze meter. The tear strength was measured in accordance with JIS P-g//A using an Elmendorff test with two incisions. The bending whitening property of the film sheet is 780°J.
J: Shows the whitening state when bent.

The display of the evaluation results is as follows.

＠ No whitening ○ No whitening △ No whitening × Whitening × υrn,ru (brittle) The contact angle was determined by the advancing contact angle (θ) with water, and was evaluated as being aqueous. (VjJ Wakosi Contact Ankle Meter Model A-P was used) IJII workability indicates film molding processability using a 10m1T-die using a 2Sφ extruder.

×L Low Δ Moderate ○ Good Refraction The refractive index was measured using an Atsube refractometer after molding a film with a thickness of about 50 μm.

Example 1 A container equipped with a cooler and a cooling device was filled with ion-exchanged water, 2 SO products, and perfluoroalkyl sulfone-rich potassium (Megafac B'-ii).

Person B's Ink Chemistry i) / 6f+, sodium formaldehyde sulfoxylate 0θS part in the lower part of the preparation chamber 4; l 4 Chitoshi, λ, 2. ．． A mixture consisting of θ parts of 2-trifluoroethyl acrylate, 1 part of 3-butylene dimethacrylate, 1 part of allyl methacrylate, and 1 part of cumene hydroperoxide was charged and heated at the same temperature for 7
After the QA was raised to 0.00, the reaction was continued for 60 minutes to complete the polymerization of the rubber shell.

Om, ulJl, a mixture consisting of 70 parts of 2-trifluoroethyl methacrylate, 1 part of allyl methacrylate, and 0.2 parts of cumene hydroperoxide.
/IJ was added dropwise over 30 minutes, and stirring was maintained for 60 minutes to complete the polymerization of the intermediate layer. More to come! , 2. J-) Lifluoroethyl methacrylate 110171s, n-octyl mercaptan 05 parts, cumene hydroperoxide 0
A mixture consisting of Q (J) was added dropwise in an amount of AO to complete the polymerization of the resin layer. The latex particle size was bx qso R.

100 polymer emulsions thus obtained were salted out using calcium chloride, washed, dried and extruded. The residual calcium content in the final polymer composition was 0.5 ppm. The obtained polymer was press-molded using Koni OC to create a 50 μm thick (Q film).

The refractive index was /, Dako/Q, and the advancing contact angle with water was 7 points. Good bendability and no whitening. V3
When the elastic behavior was measured, the E' (dyn/cT/l) elastic loss peak showed a gentle dispersion up to 2oc-qoc. The tan δ was σ] with a peak of 73C. Zengen Gekigo Transmission '4 is 90% 1 haze 2% iM
T! The film had good I4 properties, 0 tensile Ii, and breakage fat of 23%.

Example 1 A D-stage copolymer was formed into a film using the same procedure as in Example 1, except that the intermediate layer was made into two layers and the distance composition was changed.
′:! For i, the same rubber composition as in Example 1) was used. The intermediate layer was divided into one part and polymerized.

The middle 1st part of the rubber 1st side is 2. ．． 2. ．． 2-) Lifluoroethyl acrylate 7, S-to, 2,2. ．． 2-) Lifluoroethyl acrylate Y'K'fS % allyl methacrylate 0. ; Lkm, the composition was made to consist of 01 parts of cumene hydroperoxide, and the calculated Tg was 103C. The intermediate layer on the 0-phase Jlfff layer side, which was added dropwise for 75 minutes and then stirred and held for 30 minutes, was solidified.
Triple fluoroethyl acrylate toyu S, co, co, trifluoroethyl methacrylate 7s'B, allyl methacrylate o, as part, cumene hydroperoxide.

The composition was made up of 7 parts, and the calculated Tg was sgqc. The mixture was added dropwise in the 1S direction and the polymerization was completed after stirring and maintaining for 30 minutes. For the outermost resin layer, the same operation as in Example was used. The results are shown in Tables 1 and 2. The 81 bending whitening property of the film was good, there was almost no whitening, and the film still maintained extensibility.

Example 3 To change the composition by adding 3 layers of middle 1 kanno. Example 1
An S-stage co-claw assembly was manufactured by performing exactly the same operation as above. The rubber layer used the same composition rubber as in Example 1. The middle class is 3
It was divided into two parts and polymerized.

The intermediate j and j on the com Jd side are ko, 2. Coat trifluorotetraethyl acrylate 9%, 2,2.2-trifluoroethyl methacrylate 7 parts, allylmethac IJ l, -
The composition was composed of 0.2 j 1 full s and 01 part of cumene hydroperoxide, and the calculated Tg was 1 C, which was added dropwise in the 1S direction and the polymerization was completed after holding for 30 minutes. The next middle class is 2. Ko.

-monotrifluoroethyl acrylate, ? , 7! r
parts, 2.2.2-trifluoroethyl methacrylate 1.2kfff, allyl methacrylate O/λ5g,
The calculated Tg for a composition consisting of cumene hydroperoxide o, o s 56 is /0. ,? It became U.

It was added dropwise over io minutes and held for 13 minutes to complete the polymerization.

The next intermediate layer on the resin side is 2-) IJ fluoroethyl acrylate 125, 2,2.2-trifluoroethyl methacrylate) 3. '7! f5i・The composition was composed of allyl methacrylate θ/, zzfilS, and cumene hydroperoxide OO, and the calculated Tg was 9C for S. It was added dropwise over 10 minutes and held for 75 minutes to complete the polymerization. The outermost resin layer was operated in the same manner as in Example 1, and the composition was determined so that changes in each Ftj l and ij UJ T g monotonically increased. The results are shown in Tables 1 and 2.

The film had good whitening properties when folded, with no whitening observed at all.
Examples q to A which also maintained high elongation. As a rubber source in Example/, 2. ．． The results of using other fluorinated alkyl acrylates in place of 2-trifluoroethyl acrylate are 'pable -/
, ,2.

Other than that, polymerization was carried out in the same manner as in Example 1, and a film was prepared and evaluated. The results were as shown in Table 1 and Table a.

Comparative Example 1 The same operation as in Example 1 was carried out, and the rubber IW was the same as in Practical Example 1.
The remainder, )f, ij composition was conveniently used. The middle layer is coated with fluoromeroethyl methacrylate. A mixture consisting of 30% allyl methacrylate, 0.2% allyl methacrylate, and 0.2% cumene hydroperoxide was added dropwise over 3C minutes, and the polymerization was completed after stirring and maintaining for AO minutes.

Following the clearing, the resin layer is formed from Co, 21--trifluoro r1 ethyl methacrylate 30Hb, -2+-2+, 2) 0 parts of trifluoroethyl acrylate, 0 parts of n-octyl mercaptan, 0 parts of cumene hydroperoxide θlI After dropping a mixture of The strength and elongation were not sufficient.The results are shown in Table 7 and Table 2 below.

Comparative Example/Example/3FASO=S as a rubber layer,
As a resin layer, 7 F +vi 30 fivSk
One-stage polymerization was carried out without using the middle INj layer. The results are shown in Figures 1 and 1.

Example 7 The multi-stage polymer obtained in Example 3 was used as a sheath component, and polymethyl methacrylate was used as a core component, using a core-sheath spinneret to spin composite fibers using an IOC at a speed of J Om/min. I wound it up. The obtained filaments are ordered by diameter θS, core straight & 0. #? It was a dragon with concentric curved surfaces and a smooth filament surface.

What is the optical transmission loss of this filament? ts d13
/'krn, which was excellent. Furthermore, this filament was roughly placed on a mandrel with a diameter of 2, and when it was observed with a microscope, no crank was observed in the cladding part.

Claims (1)

[Claims] The inner layer is a rubber layer tA) consisting of a 7-fluorinated alkyl acrylate or a 7-fluorinated alkyl methacrylate having a glass transition temperature of OC or lower, and a fluorinated alkyl methacrylate having a glass transition temperature of σ or higher than soC. The outer layer is a tree (Ht# IsotB) consisting of a polymer as the main component, and further includes a rubber layer (A) and a resin layer (B) C1,
) A fluorinated acrylic resin multi-stage polymer comprising at least one intermediate layer tC) made of a polymer whose glass transition temperature (Tg) is higher than that of the rubber layer and lower than that of the resin layer.