JPS6142507A - Alkylated cyclohexanecarboaldehyde-acetalized polyvinyl alcohol - Google Patents

Abstract

NEW MATERIAL:An alkylated cyclohexanecarbonaldehyde-acetalized polyvinyl alcohol of the formula (wherein l>=1, m, n and p are each 0 or >=1, R is a 1-6C alkyl, g is a natural number <=3 and R' is H, a 1-10C linear aliphatic, cyclopentane, cyclohexane or aromatic group). USE:A material for disc bases or films of optical information recording media in which laser beams are utilized. PREPARATION:The titled compound is obtained by adding an alkylated cyclohexanecarboaldehyde and, optionally, a linear aliphatic, cyclopentane, cyclohexane or aromatic aldehyde to polyvinyl alcohol and effecting a condensation reaction among them.

Description

[Detailed description of the invention] (Industrial use*) Kiba F! A relates to a new polymer compound, alkylated cyclohexane carbaldehyde and doacecooled polyvinyl alcohol.More specifically, it relates to a polymer compound obtained by acetalizing polyvinyl alcohol with alkylated cyclohexane carbaldehyde. It is something.

(Prior art) Conventionally, polyvinyl 1 alcohol ν, formaldehyde,
So-called polyvinyl acecools, such as polyvinyl formal, polyvinyl acecool, and polyvinyl butyral, obtained by reacting acetaldehyde and butyraldehyde, respectively, are widely used as materials for composites, #I & fibers, or synthetic resins.

However, it has not yet been determined whether polyvinyl acecool can be obtained by reacting polyvinyl alcohol with alkylated cyclohexanecarbaldehyde.

(Problems to be Solved by the Invention) The present inventor reacted real WAK, polyvinyl alcohol, with alkylated cyclohexane aldehyde, and as a result of recognizing the properties of the obtained product, the alkylated cyclohexane carbaldahyde -Acecooled polyvinyl alcohol is obtained, which is a transparent base with outstanding shape stability! t. It was confirmed that it was a resin. The present invention was made based on this confirmation.

(Components of the Invention) The gist of the present invention is an alkylated cyclohexane compound represented by the general formula % (%), aldehyde acetalized polyvinyl alcohol,
The above integers, m, n and p are O or a chant of 1 or more, R is an alkyl group with 1 to 6 carbon atoms, q is a natural number of 3 or less, R' is hydrogen or a carbon number of 1 to 10 chain aliphatic, cyclopentane, cyclohexane or 7ct
'i represents an aromatic hydrocarbon group.

First, a method for producing the compound of formula (1) will be explained.

The above compound can be obtained by adding anosylated cyclohexanecarbaldehyde and, if necessary, a chain aliphatic, cyclobencune, cyclohexane or aromatic aldehyde to polyvinyl alcohol, and performing a condensation reaction between them.

In this condensation reaction, all aldehydes theoretically have 6
It is best to add a slight excess of up to twice the amount considered as wilting.

This combined reaction may be carried out by either the precipitation method or the dissolution method. The precipitation method uses water as a solvent, for example, and dissolves the raw material polyvinyl 1 alcohol in water.
A method for obtaining a solid powder by adding a catalyst such as an acid to perform a condensation reaction, precipitating a compound represented by formula (1) (hereinafter referred to as polyvinyl acetal), and neutralizing the acid used as a catalyst. Out. The only difference between the dissolution method and the dissolution method is that an organic solvent such as isopropanol, gukunol, or tetrahydrofuran is used as the solvent.
! Polyvinyl acecool is obtained in the form of a solid powder by dissolving it in a solvent and placing it in an insoluble liquid, such as water. In either method, the resulting powder contains impurities such as unreacted aldehyde and salts generated during neutralization, so in order to remove these impurities, ethyl alcohol or the like is used. Extract the impurities with a suitable solvent to obtain pure polyvinyl acecool.

+1) Polyvinyl acecool represented by the formula is a moiety acetalized by alkylated cyclohexanecarbaldehyde (hereinafter referred to as alkylated cyclo moiety)
It is characterized by including. It may or may not contain a monocetalized moiety (hereinafter referred to as an aliphatic moiety) with a chain aliphatic, cyclobencune, or cyclohexane-spread aromatic aldehyde. Since this polyvinyl acecool contains an alkylated cyclo moiety, as the content of the alkyl cyclo moiety increases, its heat resistance and moisture absorption resistance tend to improve. This trend is
This is a tendency that has not been observed in conventional polyvinyl acetals that only have aliphatic moieties, such as polyvinyl butycool. That is, with polyvinyl butycool and the like, when trying to improve heat resistance, there was a tendency for hygroscopicity to increase. Since the polyvinyl acetal of the present invention contains an alkylated cyclo moiety, it has the characteristics of improved moisture absorption resistance and improved heat resistance, and has good shape stability. When the composition fraction of the cyclo moiety is 10% or more, that is, z (z + m) + n + p
= 1, when l≧-yxt, polyvinyl acecool has excellent moisture absorption resistance and heat resistance, and has a small photoelastic coefficient, which is preferable, particularly when l≧iXf, and In the alkylated cyclo moiety, R is a methyl group and q is preferably 1.

R' in the aliphatic moiety may be a hydrogen atom, and
It may be a chain aliphatic group, cyclopentane, cyclohexitine, or aromatic hydrocarbon group having 1 or more carbon atoms and 1θ or less. Although the aliphatic moiety is not essential, if it is included, the ai component ratio should be 30% or less, that is, 2 (t+
When m)+n+fi=t, it is preferable that m=B x t.

In formula (1), the degree of acecoolization is z(l+m)+
When n 10p == t, z<t+m>+tx
Although it is represented by xoo, it is preferable that the degree of acecoolization of the alkylated cyclo moiety is high. Also, the degree of saponification is expressed as (100-7)+#X1oo at +112,
When the degree of saponification is 95 or more, the transparency of polyvinyl acecool is particularly good, and it is preferable that p≦pull × l.
Among these, the case where p≦π×t is particularly preferable. 7 In addition, the composition fraction of the polyvinifre alcohol part (hereinafter referred to as Hohar part) is 4096 or less, that is, n≦i
/ is preferable.

Therefore, the polyvinyl acecool of the present invention has an alkylated cyclo moiety of 10% or more, 2(1+m)+n+
When p=1, l≧iX/.

! The case where m=-Xt, n≦πxt, p≦punishment×l is preferable because it has good moisture absorption resistance, heat resistance, and excellent shape stability, and has a small photoelastic coefficient and excellent transparency. , the alkylated cyclo moiety is 301≧−X l , m=0,
The cases where n≦−Hxt and p≦g x t are particularly preferred.

In formula 111, the alkylated cyclo moiety and the fat 11
Although it is shown that the IC portions are locally combined in clusters to form a so-called block copolymer, this is only shown for the sake of simplicity; in reality, it is a compound that is randomly dispersed. The alkylated cyclohexanecarbaldehyde-acecooled polyvinyl alcohol of the present invention contains an alkylated cyclo moiety, so it has good moisture absorption resistance and heat resistance, and has a good shape. A disk substrate for an optical information recording medium using radar light, which requires excellent stability, low photoelastic coefficient, excellent transparency, low birefringence, shape stability, and optical properties. It is expected to be used as a suitable material for a variety of optical applications such as films and films, and has significantly better shape stability than polymethyl methacrylate, which has been traditionally supplied for similar applications, and has significantly better optical properties than polycarbonate. Are better.

(Example) The present invention will be explained below with reference to Examples.

<Example 1> (a) Production of polyvinyl acecool Saponification degree 99%,
Polyvinyl alcohol 100 with a weight average degree of polymerization of 1700
y was dissolved in pure water 9002. This aqueous solution was cooled to 13°C, and while stirring, concentrated hydrochloric acid (purity 35) ifi% 1-5
．． 72 was added thereto, and 14 λ1 pt of methylcyclohexanaldehyde was added dropwise over a period of 10 minutes. A precipitate was deposited 21 minutes after the start of the dropwise addition. 10 minutes after precipitation, 5L3p of salt # (purity 35% by weight) was added,
The mixture was left as it was, and after 2 hours, the temperature was raised to 60°C, and the temperature was maintained for 5 hours to obtain polyvinyl acecool.

This polyvinyl acecool was washed with pure water for 2 hours, and the polyvinyl acetal was further dispersed in 800 y of pure water for neutralization, the pH was maintained at 9.5, and stirring was continued for 4 hours.

The polyvinyl acecool thus obtained was dehydrated, socked, and extracted with n-hexitine as a solvent in an extractor all day and night to remove residual aldehyde, yielding 171f polyvinyl acecool.

(b) Confirmation of physical properties of polyvinyl acecool The degree of acetalization, residual hydroxyl groups, and remaining acetyl groups were measured for the above-mentioned polyvinyl acecool. Furthermore, the glass transition point, water absorption, light transmittance, and photoelastic coefficient of the obtained polyvinyl acecool were measured. The results are as shown in Table 1, and the optical properties were excellent, especially the glass transition point was high and the water absorption was low.

In addition, the glass transition points are D, S, C (Diffenc
ialScanning Calorimeter)
According to the measurement equipment PERKIN-ELMER ty
Measurement was performed using peDSC-IB in a measurement temperature range of 20 to 200°C.

The water absorption rate was determined by immersing the dried material in pure water at 20°C for 24 hours.
It was determined by the change in weight before and after.

Light transmittance was measured according to ASTM D-1003.

The photoelastic coefficient is determined by bending a resin plate with a thickness lsm and a width W of 4'ga with a curvature b = αO1m-'' in the width direction, and calculating the outer circumference, inner circumference, and multiple bends (P1 and ΔF2 to the order). It was determined using a polarized r4 microscope using a Qum lamp (wavelength λ is 5890 angstroms) as a light source.If the Poisson's ratio of the resin is σ, then the coefficient of birefringence for unit length index difference C5train
is calculated using the following formula.

If the Young's modulus of the resin is E, the photoelastic coefficient C5tress
It is determined by the h-order formula.

In addition, an infrared absorption spectrum was taken for the polyvinyl acecool obtained above, and the unique absorptions therein are listed as follows.

However, the m position is cm-1.

3520.295G, 2925, 2870.174G,
1455.1435, 1420, 1380, 1350.
1310% 1295, 1245, 1230% 122
0゜l 175.1140, 1115, 1085, 10
30.100G, 950.890.830,730.
710.695, 620. 415゜〈Example 2〉 (a) Production of polyvinyl acecool Saponification degree 9796
, Tnfit average + child ff 18,000 d (dispersed in a mixture of 900 p of lihinyl alcohol wofropanol, kept at 55°C with stirring, and added with concentrated hydrochloric acid (purity 35 d ff)
57.02 of methyl cyclohexanaldehyde 7L and 92 of butyraldehyde 4a were added and reacted at the same time for 12 hours. The obtained resin was dropped into 10 liters of pure water to obtain a white powder. This powder was neutralized and purified in the same manner as in Example 1 to obtain 181y polyvinyl 1cetal t-i.

(b) Confirmation of polyvinyl acecool The physical properties of the polyvinyl acecool described above were measured in exactly the same manner as in Example 1 (!). The results are also shown in Table 1.

Comparative Example 1> Butyralization was carried out in exactly the same manner as in Example 1, except that gtyraldehyde 8L7f was used instead of methylcyclohexanaldehyde, and this was further neutralized (mtp) to obtain 141/polyvinyl guccicool. Obtained. The physical properties of this polyvinyl guchicool were measured in the same manner as in Example 1. The result! It is also shown in Table 1.

Comparative Example 2> Regarding polymethyl methacrylate with a degree of polymerization of 2p00,
Glass transition point, water absorption, light transmittance and photoelastic coefficient tf
N was determined. The results are also shown in Table 1.

<Comparative Example 3> Physical properties similar to those of Comparative 4fiJ2 were measured for a reprinted polycarbonate (trade name: Panlite L-1250, manufactured by Teijin Chemicals). The results are also shown in Table 1.

Table 1 As is clear from Table 1, the polyvinyl acetal of the present invention has a higher glass transition point than polyvinyl butyral, has a lower water absorption rate, has a lower water absorption rate than polymethyl methacrylate, and has a lower water absorption rate than polycarbonate. is excellent.

Patent bi-head person Bondsui Chemical Industry Co., Ltd. Representative: Mototoshi Numa Procedural amendment (own ship) December 12, 1980

Claims (1)

[Claims] 1. Alkylated cyclohexanecarbaldehyde-acetalized polyvinyl alcohol represented by the general formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [Formula (1)]. However, l is 1
The above integers, m, n and p are 0 or an integer of 1 or more, R is an alkyl group having 1 to 6 carbon atoms, q is a natural number of 3 or less, R' is hydrogen or a carbon number of 1 to 10 represents a chain aliphatic, cyclopentane, cyclohexane or aromatic hydrocarbon group. 2. In formula (1), when 2(l+m)+n+p=t, l≧1/10×t, m≦3/10×t, n≦4
/10×t, p≦1/20×t, the alkylated cyclohexanecarbaldehyde-acetalized polyvinyl alcohol according to claim 1. 3. In formula (1), when 2(l+m)+n+p=t, l≧3/10×t, m=0, n≦4/10×t
, p≦1/50×t, the alkylated cyclohexanecarbaldehyde-acetalized polyvinyl alcohol according to claim 1. 4. The alkylated cyclohexanecarbaldehyde-acetalized polyvinyl alcohol according to claim 1, wherein in formula (1), q=1 and R is a methyl group.