JPS6021666B2 - coating composition - Google Patents
coating compositionInfo
- Publication number
- JPS6021666B2 JPS6021666B2 JP15222278A JP15222278A JPS6021666B2 JP S6021666 B2 JPS6021666 B2 JP S6021666B2 JP 15222278 A JP15222278 A JP 15222278A JP 15222278 A JP15222278 A JP 15222278A JP S6021666 B2 JPS6021666 B2 JP S6021666B2
- Authority
- JP
- Japan
- Prior art keywords
- pva
- aqueous solution
- silicic acid
- composition
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000008199 coating composition Substances 0.000 title claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 26
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 235000012239 silicon dioxide Nutrition 0.000 claims description 20
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003729 cation exchange resin Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 238000000576 coating method Methods 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 17
- 229910052681 coesite Inorganic materials 0.000 description 13
- 229910052906 cristobalite Inorganic materials 0.000 description 13
- 229910052682 stishovite Inorganic materials 0.000 description 13
- 229910052905 tridymite Inorganic materials 0.000 description 13
- 238000000034 method Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000000968 intestinal effect Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- -1 sodium silicate Chemical compound 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000013053 water resistant agent Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【発明の詳細な説明】
本発明は耐熱水性をもっポリピニルアルコール（以下Ｐ
ＶＡと略す）系塗膜組成物に関するもので、より詳しく
はＰＶＡと低ナトリウムのケイ酸水溶液を混合した塗膜
組成物に係わるものである。DETAILED DESCRIPTION OF THE INVENTION The present invention uses polypynyl alcohol (hereinafter referred to as P) having hot water resistance.
The present invention relates to coating compositions based on VA (abbreviated as abbreviated as VA), and more specifically to coating compositions containing a mixture of PVA and a low-sodium silicic acid aqueous solution.
ＰＶＡは 紙加工、繊維加工、接着剤、フィルム、成形
物等に広く用いられているが、水溶性高分子であるため
耐水性に劣りその用途に制限がある。PVA is widely used in paper processing, fiber processing, adhesives, films, molded products, etc., but since it is a water-soluble polymer, it has poor water resistance and its uses are limited.
これを解決するために種々の方法が提案されており、た
とえば熱処理、棚砂、グリオキザール等の耐水化剤の添
加、尿素メラミン樹脂等の熱硬化性樹脂の併用等が提案
されているが、耐水性が不十分であること、熱処理を必
要とすること、作業環境に問題があること、溶液の保存
安定性に欠ける等の欠点があり、実用に供する場合や塗
膜の適用条件に制約される点を多く有する。ＰＶＡ水溶
液にケイ酸ナトリウムを添加したものは常温で硬化膜を
得られるが膜が熱水との接触で膨潤し易く、加熱して硬
化膜を得ても熱水で膨溝する傾向を示す。ＰＶＡ水溶液
にコロィダルシリカ（シリカゾル、懸濁液）を添加した
ものは常温で硬化し得るが、より硬度と耐水性の膜を得
るためには１００〜２０ぴ○で１時間以内の加熱処理を
要しかくして得られた膜は熱水により膨潤する傾向を有
する。本発明はケイ酸成分を含有するＰＶＡ系塗膜組成
物（以下組成物と略す）を提供するものである。Various methods have been proposed to solve this problem, such as heat treatment, addition of water-resistant agents such as terrace sand and glyoxal, and combination use of thermosetting resins such as urea-melamine resin. There are disadvantages such as insufficient properties, heat treatment required, problems in the working environment, and lack of storage stability of the solution, which limits the practical use and application conditions of the coating film. have many points. When sodium silicate is added to a PVA aqueous solution, a cured film can be obtained at room temperature, but the film tends to swell upon contact with hot water, and even if a cured film is obtained by heating, it tends to swell with hot water. A PVA aqueous solution with colloidal silica (silica sol, suspension) can be cured at room temperature, but to obtain a film with higher hardness and water resistance, heat treatment at 100 to 20 pi for less than 1 hour is required. The membrane thus obtained has a tendency to swell with hot water. The present invention provides a PVA coating composition (hereinafter abbreviated as composition) containing a silicic acid component.
本発明は耐水性の優れた塗膜を常温で得られる組成物を
提供することである。本発明の別の目的は耐熱水性の塗
膜を得られる組成物を提供することである。本発明の別
の目的は硬度の高い塗膜を得られる組成物を提供するこ
とである。本発明はポリビニルアルコールの水溶液およ
びＳｉ０２換算濃度２なし、し８重量％のケイ酸水溶液
を混合した組成物であって、ケイ酸ナトリウム水溶液を
陽イオン交換樹脂によって脱Ｎａ十処理しケイ酸水溶液
を用いて、Ｓｉ０２対ポリビニルアルコールの重量比が
０．０５ないし０．５５であることを特徴とする塗膜組
成物を提供するものである。The object of the present invention is to provide a composition that allows a coating film with excellent water resistance to be obtained at room temperature. Another object of the invention is to provide a composition from which a hot water resistant coating can be obtained. Another object of the present invention is to provide a composition that provides a coating film with high hardness. The present invention is a composition in which an aqueous solution of polyvinyl alcohol and an aqueous silicic acid solution with a SiO2 concentration of 2 and 8% by weight are mixed, and the aqueous sodium silicate solution is treated to remove Na with a cation exchange resin to form an aqueous silicic acid solution. The present invention provides a coating composition characterized in that the weight ratio of Si02 to polyvinyl alcohol is from 0.05 to 0.55.
本発明で用いられるケイ酸水溶液はＳｉ０２濃度が８％
以下、好ましくは６〜２％である。The silicic acid aqueous solution used in the present invention has a Si02 concentration of 8%.
Below, it is preferably 6 to 2%.
更に詳しくはケイ酸ナトリウムいわゆる３号ケイ酸ナト
リウム等の水ガラスをＳｉ０２濃度を８％以下の水溶液
とし腸イオン交換樹脂で脱Ｎａ＋処理をしたものでＮａ
２０分は０．０２％以下、ｐＨ３．５〜４の範囲にある
ものである。陽イオン交換樹脂で脱Ｎａ＋する際、用い
るケイ酸ナトリウム水溶液のＳｉ０２濃度は、なるべく
高濃度の方がよいが８％以下、好ましくは６％程度が水
溶液の安定性、塗膜乾燥にすぐれたものが得られる。本
発明で用いられるＰＶＡは特に限定されるものではない
が完全ケン化型で重合度８００〜１４００の範囲のもの
が耐水性、取扱い易さがよく、水溶液の濃度としては１
５〜５％好ましくは１０％がケイ酸水溶液と混合して組
成物とするのに適当である。More specifically, water glass such as sodium silicate, so-called No. 3 sodium silicate, is made into an aqueous solution with a Si02 concentration of 8% or less, and treated with an intestinal ion exchange resin to remove Na+.
20 minutes is 0.02% or less and the pH is in the range of 3.5 to 4. When removing Na+ with a cation exchange resin, the Si02 concentration of the sodium silicate aqueous solution used should be as high as possible, but 8% or less, preferably about 6%, provides excellent stability of the aqueous solution and drying of the coating film. is obtained. The PVA used in the present invention is not particularly limited, but one that is completely saponified and has a degree of polymerization in the range of 800 to 1400 has good water resistance and ease of handling, and the concentration of the aqueous solution is 1.
5-5% preferably 10% is suitable for mixing with the aqueous silicic acid solution to form the composition.
本発明の組成物はこれらのＰＶＡ水溶液とケイ酸水溶液
とをＳｉ０２／ＰＶＡ（重量比）＝０．０５〜０．５５
の範囲、好ましくは０．１〜０．４の範囲になるごとく
混合することにより安定な組成物が得られ塗膜の耐水性
、硬度とも良好な結果を得る。Ｓｉ０２／ＰＶＡの比が
０．０５以下では塗膜の熱水時の耐水性は不十分であり
、０．５５以上では組成物の保存安定性が悪く造膜性に
劣り実用的でない。本発明の組成物は、通常の塗膜形成
法たとえば刷毛塗り、スプレー吹付浸債等の方法で塗布
し、常温にて乾燥することにより塗膜を形成できる。The composition of the present invention combines these PVA aqueous solution and silicic acid aqueous solution in a ratio of Si02/PVA (weight ratio) of 0.05 to 0.55.
By mixing in the range of 0.1 to 0.4, preferably in the range of 0.1 to 0.4, a stable composition can be obtained and good results can be obtained in both water resistance and hardness of the coating film. If the Si02/PVA ratio is less than 0.05, the water resistance of the coating film in hot water will be insufficient, and if it is more than 0.55, the composition will have poor storage stability and poor film-forming properties, making it impractical. The composition of the present invention can be applied to form a coating by a conventional coating method such as brush coating, spray coating, etc., and then dried at room temperature to form a coating.
得られる塗膜は沸騰水にも耐える耐水性を有し、鉛筆硬
度母日以上の高い硬度をもつものである。本発明のケイ
酸水溶液はケイ酸が低分子の状態で活性な水酸基をもち
、ＰＶＡの水酸基と常温乾燥といったおた、やかな条件
で相当量の脱水反応を容易に起こしＰＶＡ塗に耐水性を
付与するものと思われる。本発明の組成物は常温乾燥に
より熱水にも耐える耐水被膜を形成するものであり、紙
加工、繊維加工、接着剤等従来ＰＶＡが使用されていた
分野にさらに広く応用が可能であり、添加剤としてタル
ク等の無機質粉末や、顔料、染料等を加え塗材としても
広く利用できる。The resulting coating film has water resistance that can withstand boiling water, and has a high hardness that is higher than the hardness of a pencil. In the silicic acid aqueous solution of the present invention, silicic acid has active hydroxyl groups in a low molecular state, and it easily undergoes a considerable amount of dehydration reaction with the hydroxyl groups of PVA under mild conditions such as drying at room temperature, thereby imparting water resistance to PVA coatings. It seems that it will be granted. The composition of the present invention forms a water-resistant film that can withstand hot water when dried at room temperature, and can be applied more widely to fields where PVA has been used in the past, such as paper processing, fiber processing, and adhesives. It can be widely used as a coating material by adding inorganic powder such as talc, pigments, dyes, etc. as agents.
つぎに実施例に基づ本発明を説明する。Next, the present invention will be explained based on examples.
（本発明における濃度％はすべて重量％である。(All concentration percentages in the present invention are weight percentages.
）実施例 １
３号ケイ酸ナトリウム水溶液（Ｓｉ０２濃度６％）を腸
イオン交換樹脂（アンバーライトＩＲ−１２０）を通し
脱Ｎａ＋してケイ酸水溶液を得た。) Example 1 A No. 3 sodium silicate aqueous solution (SiO2 concentration 6%) was passed through an intestinal ion exchange resin (Amberlite IR-120) to remove Na+ to obtain a silicic acid aqueous solution.
このケイ酸水溶液はＳｉ０２濃度６％、Ｎａ２００．０
０５％、ｐＨ３．５％であった。１０％ＰＶＡ水溶液（
ＰＶＡ完全ケン化型ケン化度９８％重合度１１００）８
の重量部にケィ酸水溶液３３．４重量部を加えて混合し
組成物を造った。This silicic acid aqueous solution has a Si02 concentration of 6% and a Na200.0
05% and pH 3.5%. 10% PVA aqueous solution (
PVA completely saponified type Saponification degree 98% Polymerization degree 1100) 8
A composition was prepared by adding and mixing 33.4 parts by weight of an aqueous silicic acid solution.
この組成物のＳｉ０２／ＰＶＡ重量比は０．２５となる
。得られた組成物をガラス板上にアプリケーター（間隙
２５ｒ、移動速度１５仇岬／秒）を用いて塗布し室温に
て５時間放置乾燥した後得られた塗膜の試験を行った。
その結果を表に示す。試験項目とその方法はつぎの通り
である。他の実施例、比較例も同様に行なった。１ 造
膜性：塗布の際ののび、および膜面の状態を良、不良で
判定した。The Si02/PVA weight ratio of this composition is 0.25. The resulting composition was applied onto a glass plate using an applicator (gap 25 r, moving speed 15 m/sec), left to dry at room temperature for 5 hours, and the resulting coating film was tested.
The results are shown in the table. The test items and methods are as follows. Other Examples and Comparative Examples were carried out in the same manner. 1 Film forming property: The spread during application and the state of the film surface were judged as good or poor.
２ 耐水性：常温耐水性（常温）は、塗膜の形成された
ガラス板を常温水（室温水２０〜３ぴ０）に２独時間浸
潰した後、塗膜の状態を観察した。2 Water Resistance: Room Temperature Water resistance (room temperature) was determined by immersing the glass plate on which the coating film was formed in room temperature water (room temperature water 20-30 mm) for two hours, and then observing the state of the coating film.
耐熱水性（熱水）は、塗膜の形成されたガラス板を沸騰
水中に２時間浸潰した後の塗膜の状態を観察した。その
結果全く変化の認められないものを◎、被膜が塗布面に
残っており、白色化が認められるものを○、部分的に被
膜の溶解が認められるものを△、被膜がほとんど溶解す
るものを×とした。３ 鉛筆硬度：ＪＩＳＫ−５４０び
塗料一般試験法６．１４に準じて測定した。４ ごばん
目テスト：ガラス坂上塗膜面に１肋間隔で各１１本づつ
直交しかつガラス素地面に達する直線状の刻み目を鋭い
ナイフを用いてつくり、ＩＯＮ固のごばん目を得る。Hot water resistance (hot water) was determined by observing the state of the coating film after immersing the glass plate on which the coating film was formed in boiling water for 2 hours. As a result, ◎ indicates that no change is observed at all, ○ indicates that the film remains on the coated surface and whitening is observed, △ indicates that the film has partially dissolved, and △ indicates that the film has almost completely dissolved. × 3. Pencil hardness: Measured according to JISK-540 and Paint General Test Method 6.14. 4 Perforation test: Using a sharp knife, make 11 straight incisions perpendicular to the surface of the glass sloping paint film at one rib interval and reaching the glass base surface to obtain ION-hard perforations.
このごばん目部分にセロファン粘着テープを手で強く押
しつけて密着させ、急激に引きはがして残っているごば
ん目数を読み残り数／１００として記録した。実施例
２〜４ケイ酸水溶液の濃度、ＰＶＡ重合度、ＰＶＡ濃度
Ｓｉ０２／ＰＶＡ比を表のごとく変え他は実施例１と同
様に行なった。The cellophane adhesive tape was strongly pressed by hand to make it adhere to the rows, and then it was rapidly peeled off and the number of rows remaining was recorded as the number of remaining rows/100. Example
The same procedure as in Example 1 was conducted except that the concentration of the 2-4 silicic acid aqueous solution, the degree of PVA polymerization, and the PVA concentration Si02/PVA ratio were changed as shown in the table.
その結果を表に示す。比較例 １
ケイ酸水溶液、ＰＶＡ水溶液は実施例１と同じものを用
いＳｉ０２／ＰＶＡ比のみ０．０３に変え他は同機に行
なった。The results are shown in the table. Comparative Example 1 The same silicic acid aqueous solution and PVA aqueous solution as in Example 1 were used, only the Si02/PVA ratio was changed to 0.03, and the other conditions were the same.
その結果を表に示す。比較例 ２
ケイ酸水溶液、ＰＶＡ水溶液は実施例２と同じものを用
いＳｉ０２／ＰＶＡのみ０．６に変え他は同様に行なっ
た。The results are shown in the table. Comparative Example 2 The same silicic acid aqueous solution and PVA aqueous solution as in Example 2 were used, only Si02/PVA was changed to 0.6, and the other procedures were the same.
その結果を表に示す。比較例 ３
実施例１においてケイ酸水溶液を使用せず他は同様に行
なった。The results are shown in the table. Comparative Example 3 The same procedure as in Example 1 was carried out except that the silicic acid aqueous solution was not used.
その結果を表に示す。表 × ゃン不良The results are shown in the table. table × yan defective
Claims (1)
度２ないし８重量％のケイ酸水溶液を混合した組成物で
あつて、ケイ酸ナトリウム水溶液を陽イオン交換樹脂に
よつて脱Ｎａ＾＋処理しケイ酸水溶液を用いて、ＳｉＯ
＿２対ポリビニルアルコールの重量比が０．０５ないし
０．５５であることを特徴とする塗膜組成物。1 A composition that is a mixture of an aqueous solution of polyvinyl alcohol and an aqueous silicic acid solution with a SiO_2 concentration of 2 to 8% by weight, in which the aqueous sodium silicate solution is de-Na^+ treated with a cation exchange resin and the aqueous silicic acid solution is used. , SiO
A coating composition characterized in that the weight ratio of _2 to polyvinyl alcohol is from 0.05 to 0.55.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15222278A JPS6021666B2 (en) | 1978-12-09 | 1978-12-09 | coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15222278A JPS6021666B2 (en) | 1978-12-09 | 1978-12-09 | coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5578046A JPS5578046A (en) | 1980-06-12 |
| JPS6021666B2 true JPS6021666B2 (en) | 1985-05-29 |
Family
ID=15535745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15222278A Expired JPS6021666B2 (en) | 1978-12-09 | 1978-12-09 | coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6021666B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5118727A (en) * | 1991-03-13 | 1992-06-02 | E. I. Du Pont De Nemours And Company | Stable mixtures of colloidal silica and a film-forming polymer |
| CN104151957B (en) * | 2014-08-21 | 2016-06-29 | 苏州靖羽新材料有限公司 | A kind of interior wall coating for building |
-
1978
- 1978-12-09 JP JP15222278A patent/JPS6021666B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5578046A (en) | 1980-06-12 |
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