EP0338008A1 - Method of attaining low formaldehyde emission from surface coated objects - Google Patents

Method of attaining low formaldehyde emission from surface coated objects

Info

Publication number
EP0338008A1
EP0338008A1 EP88900397A EP88900397A EP0338008A1 EP 0338008 A1 EP0338008 A1 EP 0338008A1 EP 88900397 A EP88900397 A EP 88900397A EP 88900397 A EP88900397 A EP 88900397A EP 0338008 A1 EP0338008 A1 EP 0338008A1
Authority
EP
European Patent Office
Prior art keywords
alkyd
lacquer
peroxide
resins
percent
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.)
Ceased
Application number
EP88900397A
Other languages
German (de)
French (fr)
Inventor
Lennart Fredriksson
Sven Göthe
Otto ÖSTRÖM
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Becker Wilhelm AB
Wilh Becker AB
Original Assignee
Becker Wilhelm AB
Wilh Becker AB
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Becker Wilhelm AB, Wilh Becker AB filed Critical Becker Wilhelm AB
Publication of EP0338008A1 publication Critical patent/EP0338008A1/en
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • C09D101/16—Esters of inorganic acids
    • C09D101/18—Cellulose nitrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/16—Esters of inorganic acids
    • C08L1/18—Cellulose nitrate, i.e. nitrocellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/08—Polyesters modified with higher fatty oils or their acids, or with resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids

Definitions

  • the present invention refers to a method of attaining low formaldehyde emission from objects surface treated with clear and/or pigmented lacquers, the vehicles of which consist of wholly or in part one or several amino formaldehyde resins and which also may contain other components, commonly used in lacquers and paints, such as binders, solvents, pigments, fillers, additives, hardeners etc.
  • the European patent publication 43036 (Vianova) describes a process to decrease formaldehyde emission from acid curing alkyd-urea resin lacquers by addition of ethylene urea.
  • the effect received by this method does not last very long.
  • the addition of ethylene urea acts inhibiting on the curing process and will impair the properties of the ultimate film.
  • the purpose of the present invention is to provide a permanent decrease of formaldehyde emission from objects surface coated with compositions containing amino resins.
  • the effect of decreasing the formaldehyde emission according to the present invention depends on a reaction between an unsaturated compound, preferably a binder component e.g. an alkyd such as tall oil alkyd, DCO-alkyd or soya oil alkyd, and formaldehyde, which reaction is catalyzed by a peroxide e.g. benzoyl peroxide.
  • the appropriate composition of the surface coating composition comprises 5-70 percent by weight, preferably 10-40 percent of the unsaturated compound and 0.1-2 percent by weight, preferably 0.2-0.5 percent of the peroxide. The use of such a surface coating composition will provide an essentially decreased formaldehyde emission.
  • Surface coating according to the present invention will also give improved film properties of the coated objects regarding surface resistance towards various liquids. See Table 2.
  • the present invention is intended for surface coated objects in general, especially however objects of wood, board. particle board etc. surface coated with clear and/or pigmented lacquers containing one or several amino resins.
  • resins are urea-formaldehyde resins, melamine-form- aldehyde resins, phenolic resins, benzoguanamine resins and derivatives of these e.g. methyl or butyl ethers.
  • lacquers examples include binders such as alkyds, polyesters, polyacrylates, catalysts such as p-toluene sulphonic acid, phosphoric acid, ethylphosphoric acid and organic solvents, pigments, fillers, and additives.
  • a clear lacquer without any unsaturated compound or peroxide is prepared with the following composition:
  • Soalkyd and Soamin are manufactured by SOAB AB, M ⁇ lndal, S eden. 100 parts by volume of the lacquer are mixed with 5 parts by volume of a curing agent (38% by weight of para- toluene sulphonic acid + 2% of phosphoric acid in ethanol) and applied on glass plate, 100 g/m 2 dry film. The wet film was dried and cured for 1 hour at 50°C. After 26 days the formaldehyde emission was measured to 0.6 mg/m 3 according to the chamber method.
  • BPO benzoylperoxide
  • Chamber value after 26 days 0.6.
  • Chamber value after 20 days 0.049.
  • Chamber value after 33 days 0.045.
  • Substrate Dark, stained wood.
  • MEK methylethylketone peroxide
  • MIKP methylisobutylketone peroxide
  • ⁇ ralac are alkyd resins from DSM Resins, Holland. Exa les 18-24 Various concentration of peroxide.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

Le procédé décrit produit une faible émission de formaldéhyde à partir d'objets revêtus en surface de vernis incolores et/ou pigmentés, dans lesquels le liant se compose entièrement ou en partie d'une ou de plusieurs résines d'aminoformaldéhyde. Dans ledit procéde, les vernis peuvent également contenir d'autres composants habituellement présents dans des vernis et des peintures, tels que des résines, des solvants, des pigments, des blancs de charge, des additifs, etc. Dans ledit procédé, le vernis est en outre additionné de 5 à 70 pour cent d'un composé organique non saturé (A) et de 0,1 à 2 pour cent d'un péroxyde (B), avant l'application sur l'objet à revêtir, ces pourcentages étant calculés sur la base du poids du vernis. Un vernis contenant lesdits composants est également décrit.The process described produces a low formaldehyde emission from objects coated on the surface with colorless and / or pigmented varnishes, in which the binder consists entirely or in part of one or more aminoformaldehyde resins. In this process, the varnishes may also contain other components usually present in varnishes and paints, such as resins, solvents, pigments, charge blanks, additives, etc. In the said process, the varnish is additionally added with 5 to 70 percent of an unsaturated organic compound (A) and 0.1 to 2 percent of a peroxide (B), before application to the object to be coated, these percentages being calculated on the basis of the weight of the varnish. A varnish containing said components is also described.

Description

METHOD OF ATTAINING LOW FORMALDEHYDE EMISSION FROM SURFACE COATED OBJECTS
The present invention refers to a method of attaining low formaldehyde emission from objects surface treated with clear and/or pigmented lacquers, the vehicles of which consist of wholly or in part one or several amino formaldehyde resins and which also may contain other components, commonly used in lacquers and paints, such as binders, solvents, pigments, fillers, additives, hardeners etc.
By surface coating of e.g. wood objects, as furniture, panels, fittings etc. with lacquers or paints containing amino resins e.g. urea-formaldehyde or melamine-formaldehyde resins, a certain emission of formaldehyde to the surrounding atmosphere will appear during and after different phases of the surface treatment process. This may, under unfavourable conditions cause irritation on sensitive persons. It is true that the emission of formaldehyde from the finished object e.g. a piece of furniture, decreases with the time, and eventually practically ceases, but when conditions are unfavourable trouble may arise for several months after the surface coating process.
Different ways have been suggested to solve the problem with such formaldehyde emission. Thus, the producers of amino resins have introduced special brands of resins with a low content of so called free formaldehyde, thus giving a lower emission, but also with these resins an embarrassing formaldehyde emission may arise. The Swedish patent application 8106537-7 (Tikkurilan Varitehtaat Oy) describes a method of decreasing formaldehyde emission from particle boards by surface coating with a composition containing cyclic urea. This method however, does not solve the problem of decreasing the emission from a lacquered surface.
The European patent publication 43036 (Vianova) describes a process to decrease formaldehyde emission from acid curing alkyd-urea resin lacquers by addition of ethylene urea. However, the effect received by this method does not last very long. Furthermore, the addition of ethylene urea acts inhibiting on the curing process and will impair the properties of the ultimate film.
The purpose of the present invention is to provide a permanent decrease of formaldehyde emission from objects surface coated with compositions containing amino resins. The effect of decreasing the formaldehyde emission according to the present invention, depends on a reaction between an unsaturated compound, preferably a binder component e.g. an alkyd such as tall oil alkyd, DCO-alkyd or soya oil alkyd, and formaldehyde, which reaction is catalyzed by a peroxide e.g. benzoyl peroxide. The appropriate composition of the surface coating composition comprises 5-70 percent by weight, preferably 10-40 percent of the unsaturated compound and 0.1-2 percent by weight, preferably 0.2-0.5 percent of the peroxide. The use of such a surface coating composition will provide an essentially decreased formaldehyde emission.
Surface coating according to the present invention will also give improved film properties of the coated objects regarding surface resistance towards various liquids. See Table 2.
The present invention is intended for surface coated objects in general, especially however objects of wood, board. particle board etc. surface coated with clear and/or pigmented lacquers containing one or several amino resins. Examples of such resins are urea-formaldehyde resins, melamine-form- aldehyde resins, phenolic resins, benzoguanamine resins and derivatives of these e.g. methyl or butyl ethers.
Examples of other components usually present in such lacquers are binders such as alkyds, polyesters, polyacrylates, catalysts such as p-toluene sulphonic acid, phosphoric acid, ethylphosphoric acid and organic solvents, pigments, fillers, and additives.
The formaldehyde decreasing effect of the present invention is demonstrated by the following examples and tables where "Chamber value, mg/m3" refers to testing according to the so called chamber method: CEN TC N 76D, 1982. According to this method the object to be tested is placed under well defined conditions in a chamber with a certain air turn-over and then the equilibrium concentration of formaldehyde in air is measured in mg/m3. Description of the method can be received from Comite Europeene de Coordination des Normes, c/o Afnor, Tour Europe, CEDEX 7, 92080 Paris.
The invention is further illustrated by means of the following examples.
Example 1 Comparative example
A clear lacquer without any unsaturated compound or peroxide is prepared with the following composition:
57.3 nitrocellulose VF2, 20% in ethanol/ethylacetate
34 Soalkyd 11-628, 75% saturated synthetic fatty acid alkyd
3.4 Soamin M80 butylated mela ine resin
5.3 Soamin 888EB butylated urea resin 60%
Soalkyd and Soamin are manufactured by SOAB AB, Mδlndal, S eden. 100 parts by volume of the lacquer are mixed with 5 parts by volume of a curing agent (38% by weight of para- toluene sulphonic acid + 2% of phosphoric acid in ethanol) and applied on glass plate, 100 g/m2 dry film. The wet film was dried and cured for 1 hour at 50°C. After 26 days the formaldehyde emission was measured to 0.6 mg/m3 according to the chamber method.
Example 2
Same as example 1, but with the addition of 0.5% by weight of benzoylperoxide (BPO) to the wet paint.
Chamber value after 26 days = 0.6.
Example 3
As example 1, but with Soalkyd 11-704, an unsaturated tall oil alkyd instead of Soalkyd 11-628.
Chamber value after 18 days = 0.24.
Example 4
As example 3, but with the addition of 0.35% by weight of BPO to the wet paint.
Chamber value after 20 days = 0.049.
Example 5
On an oak-veneered particle board a lacquer with the following composition was applied. 57,3 nitrocellulose VF2, 20% 34 Soalkyd 11-704 75%, tall oil alkyd 3.4 Luwipal 044 melamine resin 5.3 Plastopal 8736, 60% urea resin 100
Addition of 0.35% BPO
Addition of catalyst as in example 1.
Application 2 x 100 g/m2 = 90 g/m2 dry film, by curtain coater. Drying 1 hour - 50°C each coat. Ttvinner: BuAc/ethanol 1:1 Luwipal 044 is n-butylated monomeric mela in resin from BASF. Plastopal 8736 is i-butylated urea resin, 60% in i-butanol, from BASF.
Chamber value after 33 days = 0.045.
TABLE 1
EX. Dry Unsaturation Peroxide Time Chamber film g/m2 days value
1 100 - - 26 0.6
2 100 - BPO 26 0.6
3 100 tall oil alkyd - 18 0.24
4 100 tall oil alkyd BPO 20 0.049
5 90 tall oil alkyd BPO 33 0.045
Table 2 Surface resistance against liquids, SIS 83 91 18,
Liguid Time Lacqiαer Ex. 3 Lacquer Ex.3 days + 1% BPO
Water 24 4 5
Ethanol 48% 16 3 4
Coffee 16 4 3
Substrate: Dark, stained wood.
Assessment of surface defects is made according to a scale
1-5, where 5 is best (no change).
Examples 6-11 Various peroxides Formulation: 57,3 NC VF2 20%
34 Soalkyd 11-875, 75% tall oil alkyd
3.4 Luwipal 044
5.3 Plastopal 8736
1.0 Peroxide 50% Table 3 Ex. Peroxide Time Chamber value days mg/m3
6 (ref.) - 21 0.15
7 BPO 21 0.05
8 MEK 21 0.10
9 MIKP 21 0.13
10 CuHP 21 0.16
11 LP 21 0.06
BPO = benzoylperoxide
MEK = methylethylketone peroxide
MIKP = methylisobutylketone peroxide
CuHP = cumenehydroperoxide
LP = laurylperoxide.
Examples 12-17 Various unsaturation.
Formulation: 57.3 NC VF2 20%
34 unsaturated alkyd, 75' 3.4 Luwipal 044 5.3 Plastopal 8736 1.0 BPO, 50%
Table 4
EX. Type Alkyd Time Chamber days value
7 (ref . )Tall oil Soalkyd 11-875 21 0.05
12 DCO Uralac S4682 21 0.07
13 Conjugated soya oil ϋralac S4683 21 0.07
14 Conjugated DCO ϋralac S4684 21 0.06
15 Techn linseed oil ϋralac S4685 21 0.07
16 Linseed/Wood oil 9:1 ϋralac S4686 21 0.06
17 Linseed/Wood oil 75:25 ϋralac S4687 21 0.06
ϋralac are alkyd resins from DSM Resins, Holland. Exa les 18-24 Various concentration of peroxide.
Formulation: 57.3 NC VF2
34 Soalkyd 11-875 3.4 Luwipal 044 5.3 Plastopal 8736
Table 5 Ex. % BPO Time Chamber value days mg/m3
18 0 23 0.15 19 0.05 23 0.13 20 0.15 23 0.10 21 0.25 23 0.07 22 0.5 23 0.06 23 1.0 23 0.06 24 1.5 23 0.06
Examples 25-32 Effect of light and darkness. The storing conditions before measuring the Chamber Value of the surfaces coated according to the invention will incluence the formaldehyde emission. Depending whether stored in light or darkness the following results are obtained:
Formulation: 57.3 NC VF2
34 Uralac 3867, 75% tall oil alkyd
3.4 Luwipal 044
5.3 Plastopal 8736
Table 6 Ex. ght/Dark Time Cha b.Val days mg/m3
25 Light 23 0.08 26 BPO 0.5 Light 25 0.04 27 Dark 19 0.16 28 BPO 0.5 Dark 22 0.09 Formulation white paint: Alkyd: soalkyd 11-875 Melanine resin: Luwipal 044 Urea resin: Plastopal 8736 Pigment: Titaniumdioxide
Alkyd: amine resin: 75:25 ϋrea:melamine resin: 50:50 NC: 3.1% VF2
Pigment volume cone (PVC): 17.6 % Solid: 63% weight
Solvent: ethanol:BuAc 10:90
Table 7
Ex. Peroxide % Light/Dark Time Chamb.Val days mg/m3
29 - - Light 19 0.06
30 BPO 0. .5 Light 19 0.05
31 - - Dark 13 0.10
32 BPO 0. .5 Dark 13 0.05

Claims

1. A method for attaining low formaldehyde emission from objects surface coated with clear and/or pigmented lacquers in which the binders wholly or in part consist of one or several amino formaldehyde resins and which lacquers also can contain other components usually present in lacquers and paints, such as other resins, solvents, pigments, fillers, additives etc. c h a r a c t e r i z e d in that from 5 to 70 percent of an unsaturated organic compound (A) and from 0.1 to 2 percent of a peroxide (B), based on the weight of the lacquer, are added to the clear and/or pigmented lacquer before its application on the object to be coated.
2. A method according to claim 1, wherein to the unsaturated organic compound (A) is a polymer.
3. A method according to claim 2, wherein the polymer is an alkyd .
4. A method according to claim 3, wherein the alkyd is a tall oil alkyd, a DCO alkyd or a soya oil alkyd.
5. A method according to any of the claims 1-4, wherein the peroxide (B) is a benzoyl peroxide.
6. Lacquer with low formaldehyde emission with binders which wholly or in part consist of one or several amino formaldehyde resins and which lacquer also can contain other components usually present in laqcuers and paints such as resins, solvents, pigments, fillers, additives etc., c h a r a c t e r i z e d in that the lacquer contains from 5 to 70 percent of an unsaturated organic compound (A) and from 0.1 to 2 percent of a peroxide (B), based on the weight of the lacquer.
7. Lacquer according to claim 6, wherein the unsaturated organic compound (A) is a polymer.
8. Lacquer according to claim 7, wherein the polymer is an alkyd.
9. Lacquer according to claim 8, wherein the alkyd is a tall oil alkyd, a DCO alkyd or a soya oil alkyd.
10. Lacquer according to any of the claims 6-9, wherein the peroxide (B) is a benzoyl peroxide.
EP88900397A 1986-12-16 1987-12-11 Method of attaining low formaldehyde emission from surface coated objects Ceased EP0338008A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE8605404 1986-12-16
SE8605404A SE459811B (en) 1986-12-16 1986-12-16 SETTING AASTADKOMMA LOW FORMALDEHYD MISSION FROM SURFACE PROCEDURES AND BEFORE SURFACE APPLICATION

Publications (1)

Publication Number Publication Date
EP0338008A1 true EP0338008A1 (en) 1989-10-25

Family

ID=20366658

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88900397A Ceased EP0338008A1 (en) 1986-12-16 1987-12-11 Method of attaining low formaldehyde emission from surface coated objects

Country Status (7)

Country Link
EP (1) EP0338008A1 (en)
DD (1) DD279682A5 (en)
FI (1) FI892938A0 (en)
HU (1) HUT50854A (en)
PL (1) PL269467A1 (en)
SE (1) SE459811B (en)
WO (1) WO1988004678A1 (en)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4814672B1 (en) * 1970-02-23 1973-05-09

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8804678A1 *

Also Published As

Publication number Publication date
SE8605404L (en) 1988-06-17
FI892938A (en) 1989-06-15
SE8605404D0 (en) 1986-12-16
FI892938A0 (en) 1989-06-15
DD279682A5 (en) 1990-06-13
PL269467A1 (en) 1988-11-24
HUT50854A (en) 1990-03-28
SE459811B (en) 1989-08-07
WO1988004678A1 (en) 1988-06-30

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