JP3984671B2 - Chemical starch for glass fiber sizing agent - Google Patents

Description

【００１９】
実施例２
実施例１で得た各試料を用い表２に示す集束剤用糊剤組成物を調製し、９μ４０８本の硝子フィラメントに塗布し、集束、巻き取り後、巻き返して得たヤーンの諸特性（粉落ち、毛羽立ち、硬度）試験を各澱粉試料について行った。結果を表１５に示す（表中◎は非常によい状態、○はよい状態、△は劣る状態、×は非常に劣る状態、Ａは普通より硬い状態、Ｂは普通の硬さの状態、Ｃは普通より柔らかい状態をそれぞれ表す）。
【表２】

【００２０】
実施例３
実施例１で得た各試料を用い表３に示す集束剤用糊剤組成物を調製し、９μ４０８本の硝子フィラメントに塗布し、集束、巻き取り後、巻き返して得たヤーンの諸特性（粉落ち、毛羽立ち、硬度）試験を各澱粉試料について行った。結果を表１５に示す（表中◎は非常によい状態、○はよい状態、△は劣る状態、×は非常に劣る状態、Ａは普通より硬い状態、Ｂは普通の硬さの状態、Ｃは普通より柔らかい状態をそれぞれ表す）。
【表３】

【００２１】
実施例４
実施例１で得た各試料を用い表４に示す集束剤用糊剤組成物を調製し、９μ４０８本の硝子フィラメントに塗布し、集束、巻き取り後、巻き返して得たヤーンの諸特性（粉落ち、毛羽立ち、硬度）試験を各澱粉試料について行った。結果を表１５に示す（表中◎は非常によい状態、○はよい状態、△は劣る状態、×は非常に劣る状態、Ａは普通より硬い状態、Ｂは普通の硬さの状態、Ｃは普通より柔らかい状態をそれぞれ表す）。
【表４】

【００２２】
実施例５
実施例１で得た各試料を用い表５に示す集束剤用糊剤組成物を調製し、９μ４０８本の硝子フィラメントに塗布し、集束、巻き取り後、巻き返して得たヤーンの諸特性（粉落ち、毛羽立ち、硬度）試験を各澱粉試料について行った。結果を表１５に示す（表中◎は非常によい状態、○はよい状態、△は劣る状態、×は非常に劣る状態、Ａは普通より硬い状態、Ｂは普通の硬さの状態、Ｃは普通より柔らかい状態をそれぞれ表す）。
【表５】

【００２３】
【表６】

【００２４】
実施例７
実施例１で得た各試料を用い表７に示す集束剤用糊剤組成物を調製し、９μ４０８本の硝子フィラメントに塗布し、集束、巻き取り後、巻き返して得たヤーンの諸特性（粉落ち、毛羽立ち、硬度）試験を各澱粉試料について行った。結果を表１５に示す（表中◎は非常によい状態、○はよい状態、△は劣る状態、×は非常に劣る状態、Ａは普通より硬い状態、Ｂは普通の硬さの状態、Ｃは普通より柔らかい状態をそれぞれ表す）。
【表７】

【００２５】
実施例８
実施例１で得た各試料を用い表８に示す集束剤用糊剤組成物を調製し、９μ４０８本の硝子フィラメントに塗布し、集束、巻き取り後、巻き返して得たヤーンの諸特性（粉落ち、毛羽立ち、硬度）試験を各澱粉試料について行った。結果を表１５に示す（表中◎は非常によい状態、○はよい状態、△は劣る状態、×は非常に劣る状態、Ａは普通より硬い状態、Ｂは普通の硬さの状態、Ｃは普通より柔らかい状態をそれぞれ表す）。
【表８】

【００２６】
実施例９
実施例１で得た各試料を用い表９に示す集束剤用糊剤組成物を調製し、９μ４０８本の硝子フィラメントに塗布し、集束、巻き取り後、巻き返して得たヤーンの諸特性（粉落ち、毛羽立ち、硬度）試験を各澱粉試料について行った。結果を表１５に示す（表中◎は非常によい状態、○はよい状態、△は劣る状態、×は非常に劣る状態、Ａは普通より硬い状態、Ｂは普通の硬さの状態、Ｃは普通より柔らかい状態をそれぞれ表す）。
【表９】

【００２７】
実施例１０
実施例１で得た各試料を用い表１０に示す集束剤用糊剤組成物を調製し、９μ４０８本の硝子フィラメントに塗布し、集束、巻き取り後、巻き返して得たヤーンの諸特性（粉落ち、毛羽立ち、硬度）試験を各澱粉試料について行った。結果を表１５に示す（表中◎は非常によい状態、○はよい状態、△は劣る状態、×は非常に劣る状態、Ａは普通より硬い状態、Ｂは普通の硬さの状態、Ｃは普通より柔らかい状態をそれぞれ表す）。
【表１０】

【００２８】
比較例１
実施例１で得た各試料を用い表１１に示す集束剤用糊剤組成物を調製し、９μ４０８本の硝子フィラメントに塗布し、集束、巻き取り後、巻き返して得たヤーンの諸特性（粉落ち、毛羽立ち、硬度）試験を各澱粉試料について行った。結果を表１５に示す（表中◎は非常によい状態、○はよい状態、△は劣る状態、×は非常に劣る状態、Ａは普通より硬い状態、Ｂは普通の硬さの状態、Ｃは普通より柔らかい状態をそれぞれ表す）。
【表１１】

【００２９】
比較例２
実施例１で得た各試料を用い表１２に示す集束剤用糊剤組成物を調製し、９μ４０８本の硝子フィラメントに塗布し、集束、巻き取り後、巻き返して得たヤーンの諸特性（粉落ち、毛羽立ち、硬度）試験を各澱粉試料について行った。結果を表１５に示す（表中◎は非常によい状態、○はよい状態、△は劣る状態、×は非常に劣る状態、Ａは普通より硬い状態、Ｂは普通の硬さの状態、Ｃは普通より柔らかい状態をそれぞれ表す）。
【表１２】

【００３０】
比較例３
実施例１で得た各試料を用い表１３に示す集束剤用糊剤組成物を調製し、９μ４０８本の硝子フィラメントに塗布し、集束、巻き取り後、巻き返して得たヤーンの諸特性（粉落ち、毛羽立ち、硬度）試験を各澱粉試料について行った。結果を表１５に示す（表中◎は非常によい状態、○はよい状態、△は劣る状態、×は非常に劣る状態、Ａは普通より硬い状態、Ｂは普通の硬さの状態、Ｃは普通より柔らかい状態をそれぞれ表す）。
【表１３】

【００３１】
比較例４
実施例１で得た各試料を用い表１４に示す集束剤用糊剤組成物を調製し、９μ４０８本の硝子フィラメントに塗布し、集束、巻き取り後、巻き返して得たヤーンの諸特性（粉落ち、毛羽立ち、硬度）試験を各澱粉試料について行った。結果を表１５に示す（表中◎は非常によい状態、○はよい状態、△は劣る状態、×は非常に劣る状態、Ａは普通より硬い状態、Ｂは普通の硬さの状態、Ｃは普通より柔らかい状態をそれぞれ表す）。
【表１４】

【表１５】

【００３２】
【発明の効果】
本発明の硝子繊維用集束剤を塗布したヤーンは、粉落ちや毛羽立ちが少なく適度の硬度を有するという優れた諸特性を有する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a modified starch for a glass fiber sizing agent. In general, when glass fibers are spun from a spinneret in the form of multifilaments, glass fibers are bundled into a bundle of yarns immediately after being spun from the spinneret and a sizing agent mainly composed of starch is applied. This is to protect the glass fiber from the effects of bending, abrasion, etc. that are received in the next process such as rewinding, twisting, winding, warping, woven fabric, etc., and preventing powder falling, fluffing, yarn breakage, etc. is there.
[0002]
[Prior art]
As a sizing agent that acts as a film forming agent, starch or a product obtained by chemically modifying starch is usually used. This is because starch has an appropriate film forming force and adhesive force, is easy to fire and deoil, and is relatively inexpensive. In addition to starch, lubricants and preservatives are added as auxiliaries to the sizing agent.
Yarns coated with such a sizing agent exhibit excellent properties and have been used so far, but various improvements have been proposed.
[0003]
As an improvement to prevent the phenomenon of migration in which specific components (generally water-soluble components) migrate to the surface when the applied sizing agent dries the wound yarn package, -35639 proposes "a sizing agent using a cross-linked etherified starch having a mean particle diameter after gelatinization of 0.5 to 10 microns, a viscosity of 5%, and a viscosity of 30 cps or less at 50 ° C as a film-forming agent" Has been.
[0004]
Japanese Patent Publication No. 4-76338 proposes a “moving-stable glass bundling paste composition using an esterified product of starch and octyl succinic anhydride or tetradecyl succinic anhydride”.
[0005]
JP-A-61-270236 also states that “starch or hydroxyalkylated product is esterified with monovalent lower fatty acid or monovalent aromatic acid, and starch molecules are decomposed with concentrated sulfuric acid. "Agent" has been proposed.
[0006]
[Problems to be solved by the invention]
The above-mentioned sizing agent disclosed in JP-B-53-35639 uses rice starch that is expensive and has a low production yield in order to reduce the average particle size after gelatinization to 0.5 to 10 microns, or suppress swelling. The degree of crosslinking must be increased. However, highly cross-linked starch does not dissolve in water, so the film properties are poor and the film does not become a uniform and flexible film, so that the coating of the yarn is insufficient, and powder falling and fluffing increase.
[0007]
The sizing agent of the above Japanese Patent Publication No. 4-76338 uses starch with high emulsifying power having hydrophobicity and hydrophilicity, so that the oil component used in combination is emulsified with a component that is easily soluble in water, and starch paste. Migration may be difficult because the liquid and oil are integrated. However, since it moves to the surface layer of the starch film and improves the slip of the starch film surface to reduce the frictional resistance, the oil component of the role of suppressing powder falling and fluffing is emulsified and distributed also in the inner layer of the starch film, The effect of suppressing fuzz becomes poor.
[0008]
The sizing agent described in JP-A-61-270236 has a very high solubility in water because the starch is hydroxyalkylated and esterified or esterified and further subjected to acid hydrolysis with concentrated sulfuric acid. Since it is high, it is easy to migrate.
[0009]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that, as with a modified starch having a viscosity of 2 to 4 CPS at 60 ° C. in a 5% aqueous solution at 40 to 60 % by weight based on the total modified starch. It has been found that a modified starch for a glass fiber sizing agent comprising a modified starch having a viscosity of 8 to 20 CPS in a 5% aqueous solution of 60 to 40 % by weight at 60 ° C. is effective in solving the above-mentioned problems.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Glass modified starch for the fiber collecting agent of the present invention, 40 to 60% by weight of 60 ° C. for all modified starch, the same 60 to 40% by weight and modified starch having a viscosity of 2 to 4 CPS with 5% aqueous solution 60 It is a blend of two types of modified starches having different viscosities (molecular weight) consisting of a modified starch having a viscosity of 8 to 20 CPS in a 5% aqueous solution at 5 ° C. These may be blended before gelatinization, may be blended after gelatinization, or may be blended after gelatinization.
These modified starches are subjected to one or more kinds of modification selected from the group of hydrolysis treatment, etherification, esterification, grafting, and crosslinking treatment as necessary.
[0011]
The kind of starch used as a raw material is selected from corn starch, tapioca starch, wheat starch, sweet potato starch, potato starch or high amylose corn starch.
[0012]
The modified starch of the present invention is hydrolyzed as necessary. Hydrolysis is a hydrolytic treatment with a mineral acid or organic acid such as sulfuric acid, nitric acid or hydrochloric acid, hydrogen peroxide, sodium hypochlorite. This refers to hydrolysis treatment with an oxidizing agent. The degree of hydrolysis is indicated by the viscosity resulting from hydrolysis to lower viscosity (lower molecular weight). The viscosity is lowered to two levels: one having a viscosity of 2-4 CPS at 60 ° C. and 5% aqueous solution and one having a viscosity of 8-20 CPS at 60 ° C., 5% aqueous solution. The modified starch for glass fiber sizing agent of the present invention is a blend of two types of modified starches having different viscosities (molecular weight).
[0013]
In addition to the hydrolysis treatment, the modified starch of the present invention is subjected to one or more kinds of modification selected from the group of etherification, esterification, grafting, and crosslinking treatment as necessary. Etherification includes carboxymethylation, hydroxyalkylation, alkylation, benzylation, cationic etherification and the like. Of these, hydroxyalkylation is particularly effective. Hydroxyalkylation is obtained by reacting starch with 1 · 2-alkylene oxide, ie, ethylene oxide, 1 · 2-propylene oxide, or 1 · 2-butylene oxide. These alkylene oxides are added to corn starch, tapioca starch, wheat starch, sweet potato starch, and potato starch so that the MS value is in the range of 0.03 to 0.26, preferably 0.07 to 0.20. The high amylose corn starch is added so that the MS value is in the range of 0.07 to 0.36, preferably 0.10 to 0.30. Here, the MS value indicating the degree of hydroxyalkylation means the number of moles (Molar Substitution) of hydroxyalkyl groups per anhydroglucose residue of starch.
[0014]
Esterification includes acetate ester, phosphate ester, sulfate ester, nitrate ester, xanthate ester, etc. Among them, acetate ester is effectively used. The degree of esterification is such that the DS value is 0.03 to 0.26, preferably 0.07 to 0.20 for corn starch, tapioca starch, wheat starch, sweet potato starch, and potato starch. It is added to the high amylose corn starch so that the DS value is in the range of 0.07 to 0.36, preferably 0.10 to 0.30. Here, the DS value indicating the degree of esterification refers to the number of substituted ester groups per anhydroglucose residue of starch (Degree of Substitution).
[0015]
Grafting is performed by graft polymerization of one or more radically polymerizable monomers such as vinyl acetate, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, acrylamide, styrene, maleic acid, and crotonic acid. Obtained. The polymerization is carried out wet or dry using a normal radical polymerization catalyst.
[0016]
The modified starch for a glass fiber sizing agent of the present invention can be adjusted in viscosity by a crosslinking reaction in combination with the hydrolysis treatment, etherification, esterification, and grafting. As the crosslinking agent, a reagent having two or more functional groups capable of reacting with a hydroxyl group of starch such as epichlorohydrin, sodium trimetaphosphate, cyanuric chloride, adipic-acetic anhydride, formalin, diepoxide compound, and dialdehyde compound is used. It is done.
[0017]
The modified starch for glass fiber sizing agent of the present invention becomes a composition for glass fiber sizing agent by adding and mixing lubricants, softeners, preservatives and other auxiliaries usually used in the glass fiber sizing agent. Used by applying to glass filament.
[0018]
【Example】
Example 1
Corn starch acid hydrolyzed starch (Sample Nos. 1 and 2), tapioca starch oxidized / acetated starch (Sample Nos. 3 and 4), wheat starch cross-linked / hydroxypropylated / acid-treated starch (sample No.) 5, 6), acid-treated and grafted starch of sweet potato starch (sample numbers 7, 8), hydroxyethylated oxidized starch of potato starch (sample numbers 9, 10), and hydroxypropylated oxidized starch of high amylose corn starch (sample) Nos. 11 and 12) were produced. Their viscosity and degree of reaction are shown in Table 1.
[Table 1]

[0019]
Example 2
Using each sample obtained in Example 1, a sizing agent composition for sizing agent shown in Table 2 was prepared, applied to 9 μ408 glass filaments, and after bundling, winding, and various properties of the yarn obtained by winding (powder) A drop, fluff, hardness) test was performed on each starch sample. The results are shown in Table 15 (in the table, ◎ is a very good state, ○ is a good state, Δ is a poor state, × is a very poor state, A is a harder than normal state, B is a normal hard state, C Represents a softer state than normal).
[Table 2]

[0020]
Example 3
Using each sample obtained in Example 1, a sizing agent composition for sizing agent shown in Table 3 was prepared, applied to 9 μ408 glass filaments, and after bundling, winding, and various properties of the yarn obtained by winding (powder) A drop, fluff, hardness) test was performed on each starch sample. The results are shown in Table 15 (in the table, ◎ is a very good state, ○ is a good state, Δ is a poor state, × is a very poor state, A is a harder than normal state, B is a normal hard state, C Represents a softer state than normal).
[Table 3]

[0021]
Example 4
Using each sample obtained in Example 1, a sizing agent composition for a sizing agent shown in Table 4 was prepared, applied to 9 μ408 glass filaments, and after bundling, winding, and various properties of the yarn (winding) A drop, fluff, hardness) test was performed on each starch sample. The results are shown in Table 15 (in the table, ◎ is a very good state, ○ is a good state, Δ is a poor state, × is a very poor state, A is a harder than normal state, B is a normal hard state, C Represents a softer state than normal).
[Table 4]

[0022]
Example 5
Using each sample obtained in Example 1, a sizing agent composition for a sizing agent shown in Table 5 was prepared, applied to 9 μ408 glass filaments, and after bundling, winding, and various properties of the yarn obtained by rewinding (powder) A drop, fluff, hardness) test was performed on each starch sample. The results are shown in Table 15 (in the table, ◎ is a very good state, ○ is a good state, Δ is a poor state, × is a very poor state, A is a harder than normal state, B is a normal hard state, C Represents a softer state than normal).
[Table 5]

[0023]
[Table 6]

[0024]
Example 7
Using each sample obtained in Example 1, a sizing agent composition for a sizing agent shown in Table 7 was prepared, applied to 9 μ408 glass filaments, and after bundling, winding, and various properties of the yarn (winding) A drop, fluff, hardness) test was performed on each starch sample. The results are shown in Table 15 (in the table, ◎ is a very good state, ○ is a good state, Δ is a poor state, × is a very poor state, A is a harder than normal state, B is a normal hard state, C Represents a softer state than normal).
[Table 7]

[0025]
Example 8
Using each sample obtained in Example 1, a sizing agent composition for a sizing agent shown in Table 8 was prepared, applied to 9 μ408 glass filaments, and after bundling, winding, and various properties of the yarn obtained by rewinding (powder) A drop, fluff, hardness) test was performed on each starch sample. The results are shown in Table 15 (in the table, ◎ is a very good state, ○ is a good state, Δ is a poor state, × is a very poor state, A is a harder than normal state, B is a normal hard state, C Represents a softer state than normal).
[Table 8]

[0026]
Example 9
Using each sample obtained in Example 1, a sizing agent composition for a sizing agent shown in Table 9 was prepared, applied to 9 μ408 glass filaments, and after bundling, winding, and various properties of the yarn (winding) A drop, fluff, hardness) test was performed on each starch sample. The results are shown in Table 15 (in the table, ◎ is a very good state, ○ is a good state, Δ is a poor state, × is a very poor state, A is a harder than normal state, B is a normal hard state, C Represents a softer state than normal).
[Table 9]

[0027]
Example 10
Using each sample obtained in Example 1, a sizing agent composition for a sizing agent shown in Table 10 was prepared, applied to 9 μ408 glass filaments, and after bundling, winding, and various properties of the yarn obtained by rewinding (powder) A drop, fluff, hardness) test was performed on each starch sample. The results are shown in Table 15 (in the table, ◎ is a very good state, ○ is a good state, Δ is a poor state, × is a very poor state, A is a harder than normal state, B is a normal hard state, C Represents a softer state than normal).
[Table 10]

[0028]
Comparative Example 1
Using each sample obtained in Example 1, a sizing agent composition for sizing agent shown in Table 11 was prepared, applied to 9 μ408 glass filaments, and after bundling, winding, and various properties of the yarn obtained by winding (powder) A drop, fluff, hardness) test was performed on each starch sample. The results are shown in Table 15 (in the table, ◎ is a very good state, ○ is a good state, Δ is a poor state, × is a very poor state, A is a harder than normal state, B is a normal hard state, C Represents a softer state than normal).
[Table 11]

[0029]
Comparative Example 2
Using each sample obtained in Example 1, a sizing agent composition for a sizing agent shown in Table 12 was prepared, applied to 9 μ408 glass filaments, and after bundling, winding, and various properties of the yarn obtained by rewinding (powder) A drop, fluff, hardness) test was performed on each starch sample. The results are shown in Table 15 (in the table, ◎ is a very good state, ○ is a good state, Δ is a poor state, × is a very poor state, A is a harder than normal state, B is a normal hard state, C Represents a softer state than normal).
[Table 12]

[0030]
Comparative Example 3
Using each sample obtained in Example 1, a sizing agent composition for a sizing agent shown in Table 13 was prepared, applied to 9 μ408 glass filaments, and after bundling, winding, and various properties of the yarn (winding) A drop, fluff, hardness) test was performed on each starch sample. The results are shown in Table 15 (in the table, ◎ is a very good state, ○ is a good state, Δ is a poor state, × is a very poor state, A is a harder than normal state, B is a normal hard state, C Represents a softer state than normal).
[Table 13]

[0031]
Comparative Example 4
Using each sample obtained in Example 1, a sizing agent composition for a sizing agent shown in Table 14 was prepared, applied to 9 μ408 glass filaments, and after bundling, winding, and various properties of the yarn obtained by rewinding (powder) A drop, fluff, hardness) test was performed on each starch sample. The results are shown in Table 15 (in the table, ◎ is a very good state, ○ is a good state, Δ is a poor state, × is a very poor state, A is a harder than normal state, B is a normal hard state, C Represents a softer state than normal).
[Table 14]

[Table 15]

[0032]
【The invention's effect】
The yarn coated with the sizing agent for glass fibers of the present invention has excellent properties such that it does not fall off or fuzz and has an appropriate hardness.

Claims (1)

40-60% by weight of 60 ° C. for all modified starch, also 60 to 40 wt% of 60 ° C. and modified starch having a viscosity of 2 to 4 CPS with 5% aqueous solution, viscosity of 8 to 20 CPS with 5% aqueous solution A modified starch for a glass fiber sizing agent comprising a modified starch comprising