JP2001107010A - Adhesive for substrate having silanol residue in its surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide adhesives having biodegradability and transparency and strong adhesion to a substrate having silanol residues in its surface. SOLUTION: An adhesive for a substrate having silanol residues in its surface has, as the major component, a sugar chain polymeric compound represented by the formula, wherein G is a sugar residue; the hydroxyl groups in G which do not participate in polymerization may be substituted with an ester group; R is a 4-14C aliphatic hydrocarbon group or a 4-14C aliphatic hydrocarbon group whose hydrogen atom is substituted with another group; and n is a degree of polymerization and an integer of 1-5,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive containing a sugar chain polymer compound as a main component, and more particularly, to an adhesive having excellent biodegradability and transparency, and having a high degree of adhesion to a substrate having silanol residues on the surface. The present invention relates to an adhesive having adhesion.

[0002]

2. Description of the Related Art Typical examples of a substrate having a silanol residue (Si-OH group) on its surface (hereinafter referred to as "silanol-containing substrate") include glass and ceramic. As an adhesive for bonding these substrates, -OH
Polymers having polar groups such as groups, -COOH groups, -C = O groups, and -COOR groups are often used. Adhesives having these polar groups exhibit high adhesive strength with silanol residues on the surface of the silanol-containing substrate. For example, as an adhesive for bonding glass to each other, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), polyvinyl butyral resin, cyanoacrylate resin, epoxy resin, unsaturated polyester resin , Silicone resins, urethane resins and the like are known.

[0003] However, although these adhesives have good adhesive strength to glass, most of the adhesives are not decomposed when disposed of as landfill as waste.
It remained in the soil for a long time, which caused environmental pollution.

[0004]

In recent years, global environmental pollution has become apparent, and it has become necessary to consider the environment when disposing of industrial waste and household waste. Although molecular compounds have been energetically developed, there is an increasing demand for biodegradable adhesives for bonding silanol-containing substrates such as glass.

As described above, when the glass using the conventional glass adhesive is landfilled, most of the adhesive is not decomposed and remains in the soil for a long period of time. Was causing contamination. However, if the adhesive has biodegradability, the burden on the environment can be reduced even when the adhesive is disposed of as landfill or waste. Therefore, an object of the present invention is to solve the above-mentioned problems in the prior art, and to provide an adhesive that reduces environmental load.

[0006]

The above object is achieved by the present invention described below. That is, the present invention provides an adhesive for a substrate having a silanol residue on its surface (hereinafter referred to as “silanol”), which comprises a sugar chain polymer compound represented by the following general formula (I) as a main component. Adhesive for containing base material ").

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That is, the present inventors have conducted various studies on a sugar chain polymer compound which is a copolymer of a saccharide and a dicarboxylic acid. As a result, the sugar chain polymer compound shows biodegradability and a silanol-containing group. The present inventors have found that they have an excellent adhesive ability to materials, and have reached the present invention.

[0008] The sugar chain polymer compound represented by the general formula (I) having a hydroxyl group which is a polar group rich in a sugar residue (G in the general formula (I)) is a compound having a silanol residue on the surface of the silanol-containing base material. It has high adhesion to the base and can be effectively used as an adhesive for silanol-containing substrates.
Further, even in the case of a sugar chain polymer compound in which a hydroxyl group in a sugar residue is substituted with an ester group, since a high adhesive force is exerted between the ester group, which is a polar group, and the silanol residue, the silanol-containing substrate is still used. It can be effectively used as a bonding adhesive. Further, the adhesive for a silanol-containing substrate of the present invention,
Since biodegradation occurs in soil and compost, the environmental load can be reduced.

[0009]

Next, the present invention will be described in more detail with reference to preferred embodiments. The adhesive for a silanol-containing substrate using the sugar chain polymer compound represented by the general formula (I) of the present invention will be described in detail. The sugar chain polymer compound as a main component of the adhesive for a silanol-containing substrate of the present invention has a structure represented by the general formula (I).

[0010]

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The sugar chain polymer represented by the general formula (I) includes, for example, a hydroxyl group of a saccharide and COOH of a dicarboxylic acid.
Group, an acid anhydride group of a dicarboxylic anhydride, or a COCl group of a dicarboxylic acid chloride to form an ester bond, or a method of transesterifying a dicarboxylic acid ester with a saccharide, or using an enzymatic reaction It can be synthesized by a method such as The weight average molecular weight of the sugar chain polymer compound represented by the general formula (I) thus obtained is preferably 1,000 to 1,000.
3,000,000, more preferably 8,000-90
It is about 0000. Here, n represents the degree of polymerization,
It is an integer of 5,000.

The saccharides usable in the present invention include, for example, maltose, lactose, cellobiose,
Isomaltose, chitobiose, nigerose, trehalose, melibiose, cellotriose, chitotriose, maltotriose, cellotetraose, chitotetraose, maltotetraose, cellopentaose, maltopentaose, chitopentaose, cellohexaose, maltohexaose And oligosaccharides such as chitohexaose; monosaccharides such as glucopyranose, mannopyranose and galactopyranose; polysaccharides such as cellulose, starch, glycogen, galactan, mannan, chitin, chitosan, polyglucosamine and pullulan. Further, all or a part of the hydroxyl groups of these saccharides may be substituted with an ester group such as an acetyl group.

As the dicarboxylic acid, a dicarboxylic acid whose main chain is an aliphatic hydrocarbon group having 4 to 14 carbon atoms is used, and the main chain of this dicarboxylic acid may be substituted with another group. . Such dicarboxylic acids include, for example, acipic acid, suberic acid, azelaic acid, sebacic acid, dodecandioic acid and the like. Further, as described above, the acid anhydride or acid chloride of the above dicarboxylic acid can be used in the reaction with the saccharide. Accordingly, R in the general formula (I) is a residue obtained by removing a carboxyl group from these dicarboxylic acids or dicarboxylic acid derivatives.

Since the sugar chain polymer compound represented by the general formula (I) thus obtained has abundant polar hydroxyl groups in the sugar residue, the silanol residue on the surface of the silanol-containing base material is high. Since it has a high adhesion between the adhesive and the adhesive, it can be effectively used as an adhesive for a silanol-containing substrate. or,
Even when the hydroxyl group in the sugar residue is replaced with an ester group, it still has a high adhesive force between the ester group, which is a polar group, and the silanol residue, and therefore has a sufficient function as an adhesive for a silanol-containing base material. Can be fulfilled.

Examples of the silanol-containing substrate to which the adhesive of the present invention is adhered include glass such as quartz glass and soda lime glass, and ceramics having a silanol residue on the surface of the substrate. The adhesive for a silanol-containing substrate of the present invention is not particularly limited as long as it contains the sugar chain polymer compound represented by the general formula (I) as a main component, and various known adhesives may be used as long as the adhesiveness is not impaired. Additives can be used as needed.

The adhesive for a silanol-containing substrate of the present invention comprises:
Since it has good transparency and a relatively low melting point, it is particularly easily heat-fused with glass among silanol-containing substrates, and is suitable for bonding glass. It is biodegradable in soil and compost, and has good biodegradability. In addition, since the sugar chain polymer compound, which is the main component, is composed of saccharides and aliphatic dicarboxylic acids, it has little effect on the environment in terms of disposal and the like. Is an environmentally compatible adhesive.

[0017]

The present invention will be described more specifically with reference to Synthesis Examples and Examples. (Synthesis Example) An example of synthesis of the sugar chain polymer compound used in this example is shown below. Synthesis Example 1 A synthesis scheme of a sugar chain polymer compound used in this example is shown in the following (Formula 3).

[0018]

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25 g of anhydrous maltose (trade name: Finetose-F, manufactured by Hayashibara) was placed in a mixed solvent of 150 ml of N, N-dimethylformamide (DMF) and 30 ml of pyridine, and heated to 80 ° C. Here, 80 ml of DMF solution containing 20 ml of sebacic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
Was slowly added dropwise and stirred for 2 hours. After the completion of the reaction, the reaction solution was concentrated, and the concentrate was poured into water to obtain a precipitate.
The precipitate is washed successively with diethyl ether and then with water, filtered, dried and dried with polysebacoil maltose 35.
g (hereinafter, referred to as “Compound No. I-1”) was obtained.

When the molecular weight of the polysebacoil maltose synthesized as described above was measured by gel permeation chromatography (GPC) under the following conditions, the weight average molecular weight was 100,000 in terms of polysaccharide. there were.

<Conditions for GPC Measurement> Apparatus: HLC-8020 (manufactured by Tosoh Corporation) Column: Two Mixed-CX (manufactured by Polymer Laboratories) Eluent: DMF containing 0.1% LiBr Column oven temperature: 50 ° C.

Next, FT-IR FTS135 (BIO RAD) was used for the above polysebacoil maltose.
Was measured by the KBr tablet method. As a result, as shown in FIG.
OH stretch peak at cm ^-1 , C = O at 1,751 cm ^-1
Stretching peak, CH stretching peak of methylene group derived from sebacic acid at 2,938 cm ^-1 and 2,859 cm ^-1 , 1,2
The observation of the ester-derived C—O stretching peak at 20 cm ⁻¹ suggested that the desired sugar chain polymer was obtained. Furthermore, FT-NMR DPX400
When ¹³ C-NMR was measured using (manufactured by Bruker), 173 ppm of carbonyl carbon derived from sebacic acid and 25 ppm and 34 ppm of methylene carbon derived from sebacic acid were observed. From the above measurement results, it was confirmed that the intended polysebacoil maltose was synthesized.

(Biodegradability Test) A thermoformed sheet (thickness: 100 μm) is prepared by hot pressing the polysebacoil maltose synthesized in Synthesis Example 1, and the sheet is placed in the soil (in Canon Central Research Laboratory). , Depth 50c
m, and a biodegradability test by embedding in soil was performed. As a result, it was confirmed that the buried sheet was completely decomposed after about three months.

Synthesis Example 2 As shown in (Chemical Formula 3), 6 g of sodium acetate and 110 ml of acetic anhydride were added to 14 g of polysebacoil maltose synthesized in Synthesis Example 1, and the mixture was heated and stirred at 130 ° C. for 5 hours.
After cooling to room temperature, the reaction mixture was poured into ice water and stirred for several hours. After thoroughly washing with water, the mixture was filtered and dried, and 21 g of acetylated polysebacoyl maltose (hereinafter referred to as “Compound No.
-2 ". )was gotten.

The molecular weight was measured by GPC in the same manner as in Synthesis Example 1. As a result, the weight average molecular weight was 150,000.
The measured infrared absorption spectrum in the same manner as in Synthesis Example 1, as shown in FIG. 2, 3,460cm ^-1 vicinity of O-
Since no H stretching peak was observed, it was suggested that the hydroxyl group was acetylated. Further, Synthesis Example 1
When ¹³ C-NMR was measured in the same manner as in
Of acetyl group derived from acetyl group, and 21 ppm of methyl carbon derived from acetyl group were observed. From the above measurement results, it was confirmed that the intended acetylated polysebacoil maltose was synthesized.

(Biodegradability Test) A thermoformed sheet was prepared from the acetylated polysebacoil maltose synthesized in Synthesis Example 2 in the same manner as in Synthesis Example 1, and a biodegradability test was performed. As a result, it was confirmed that the buried sheet was completely decomposed after about three months. Synthesis Example 3 Synthesis Examples 1 and 2 except that maltose and sebacic acid used in Synthesis Example 1 were changed to the combinations shown in Table 1 below.
A sugar chain polymer compound was synthesized by the same method as described above.
Table 1 shows the molecular weight of the obtained sugar chain polymer compound. or,
The obtained sugar chain polymer compound was evaluated in the same manner as in the above biodegradability test. Table 1 shows the results.

[0027]

[Table 1]

<Examples 1 to 22> Adhesion strength, biodegradability and transparency were evaluated using the sugar chain polymer compounds synthesized in the above Synthesis Examples 1, 2 and 3 as hot melt type adhesives. . Further, a comparative example was given, and comparative verification with the example was performed. (Preparation of Sample) Synthesis Examples 1, 2 and 3
Sugar chain polymer compounds (Compound Nos. I-1 to I-1)
-22), and 0.2 by melt extrusion.
The adhesive coating was laminated to a thickness of mm. On top of this, the same sheet of glass was superimposed and heated at 120 ° C, 2 kg /
Heating and pressurizing were performed for 5 minutes under the condition of cm ² , and two glass plates were bonded to each other to obtain a sample.

(Evaluation of Adhesive Strength) With respect to each sample piece (20 mm × 10 mm) on which two glass sheets were bonded, the shear peeling force was measured. The pulling speed at this time is
50 mm / min. Met. Table 2 shows the test results of the adhesive strength. (Evaluation of biodegradability) Each sample was buried in soil and biodegraded, whereby the adhesive was decomposed and two glass plates were peeled off. Table 2 shows the test results of the biodegradability. (Evaluation of Transparency) Each sample was visually observed, and the level of transparency was evaluated on a three-point scale. Transparent ones were evaluated as 、, slightly cloudy ones as Δ, and cloudy ones as X. Table 2 shows the test results.

<Comparative Example 1> An ethylene-vinyl acetate copolymer adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., trade name: Takemelt SD-181) was used as the adhesive, and the thickness of the adhesive film was set to 0.1.
The evaluation was made in the same manner as in Examples 1 to 22, with the distance being 2 mm. <Comparative Example 2> As an adhesive, an epoxy adhesive (manufactured by Ciba Geigy, trade name: Araldite AER280) was used.
The thickness of the adhesive film was set to 0.2 mm, and the evaluation was performed in the same manner as in Examples 1 to 22. <Comparative Example 3> A silicone adhesive (manufactured by Konishi, trade name: Bond MOS-7) was used as the adhesive, the thickness of the adhesive film was 0.2 mm, and evaluation was performed in the same manner as in Examples 1 to 22. went.

[0031]

[Table 2] As shown in Table 2, the adhesive for a silanol-containing substrate of the present invention has excellent adhesive strength, and is excellent in biodegradability and transparency.

[0032]

Industrial Applicability The adhesive for a silanol-containing base material containing a sugar chain polymer compound as a main component of the present invention exhibits excellent adhesive strength to a glass substrate which is a silanol-containing base material, and has a high biodegradability. It has transparency. Further, since the sugar chain polymer compound, which is a main component of the adhesive for a silanol-containing base material of the present invention, is composed of a saccharide and an aliphatic dicarboxylic acid, it has little effect on the environment in terms of disposal and the like. ,
The adhesive for a silanol-containing substrate of the present invention is an adhesive having high environmental compatibility.

[Brief description of the drawings]

FIG. 1 is a view showing an infrared absorption spectrum of a sugar chain polymer compound (Compound No. I-1) synthesized in Synthesis Example 1.

FIG. 2 is a view showing an infrared absorption spectrum of a sugar chain polymer compound (Compound No. I-2) synthesized in Synthesis Example 2.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08B 37/00 C08B 37/00 GF Term (Reference) 4C057 BB02 BB04 DD03 HH02 4C090 AA10 BA24 BA26 BA46 BB02 BB03 BB52 BB65 BB97 DA08 DA31 4J040 ED021 ED051 GA05 GA08 GA10 JA06 JB01 LA06 LA11 MA04 MA05

Claims (5)

[Claims] 1. An adhesive for a base material having a silanol residue on its surface, comprising a sugar chain polymer compound represented by the following general formula (I) as a main component. Embedded image 2. The adhesive according to claim 1, wherein the substrate having a silanol residue on its surface is glass or ceramic. 3. The adhesive according to claim 1, wherein G in the general formula (I) is an oligosaccharide residue. 4. The adhesive according to claim 1, wherein G in the general formula (I) is a monosaccharide residue. 5. The adhesive according to claim 1, wherein G in the general formula (I) is a polysaccharide residue.